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>>> '{:02}'.format('a')
Traceback (most recent call last):
 File "<stdin>", line 1, in <module>
ValueError: '=' alignment not allowed in string format specifier
>>>
according to http://docs.python.org/py3k/library/string.html#formatspec
the default alignment is '<' or '>'

found a small string in the doc about zero padding, which enables alignment equal to =

As I read the docs, the error message is correct and this issue is invalid as a behavior issue. I read the OP's second message as more or less saying this also.
"'=' 	Forces the padding to be placed after the sign (if any) but before the digits. This is used for printing fields in the form ‘+000000120’. This alignment option is only valid for numeric types."
"If the width field is preceded by a zero ('0') character, this enables zero-padding. This is equivalent to an alignment type of '=' and a fill character of '0'."
So ":02" is equivalent to ":0=2", which is invalid.
>>> '{:02d}'.format(1)
'01'
works fine.
I decided make this a doc issue and add " for numeric types" after "this enables zero-padding" before closing this.

New changeset 85cd54b2d3a1 by Terry Jan Reedy in branch '2.7':
Issue 15660: Clarify 0 prefix for width field in str.format doc.
http://hg.python.org/cpython/rev/85cd54b2d3a1
New changeset 6bc14974024f by Terry Jan Reedy in branch '3.2':
Issue 15660: Clarify 0 prefix for width field in str.format doc.
http://hg.python.org/cpython/rev/6bc14974024f
New changeset f181dd088e63 by Terry Jan Reedy in branch 'default':
Merge with 3.2 #15660
http://hg.python.org/cpython/rev/f181dd088e63 

This came up again on python-list today in thread "Replace weird error message?" by "the.gerenuk--- via Python-list". After reading the discussion, I decided that expecting someone to read and connect together two sentences half a page apart is expecting a bit too much.
'''
'=' 	Forces the padding to be placed after the sign (if any) but before the digits. This is used for printing fields in the form ‘+000000120’. This alignment option is only valid for numeric types.
'''
Add "It becomes the default when '0' precedes the field width."
''' 
Preceding the width field by a zero ('0') character enables sign-aware zero-padding for numeric types. This is equivalent to a fill character of '0' with an alignment type of '='.
'''
This is not true when an explicit alignment other than '=' is given.
>>> "{:09}".format(-1)
'-00000001'
>>> "{:>09}".format(-1) # 2.7.11 and 3.5.1
'0000000-1'
Proposal: Replace with
'''
When no explicit alignment is given, preceding the width field by a zero ('0') character enables sign-aware zero-padding for numeric types. This is equivalent to a fill character of '0' with an alignment type of '='.
'''
I presume the problem with changing the error message is that it is not immediately known that alignment was set implicitly, by 0 before decimal width, rather than explicitly. If the spec string is still available, it could be searched and the message adjusted if '=' is not present. That proposal should be a new issue if someone wants to push it.

> '''
> When no explicit alignment is given, preceding the width field by a zero ('0') character enables sign-aware zero-padding for numeric types. This is equivalent to a fill character of '0' with an alignment type of '='.
> '''
I think that's good.
> I presume the problem with changing the error message is that it is not immediately known that alignment was set implicitly, by 0 before decimal width, rather than explicitly. If the spec string is still available, it could be searched and the message adjusted if '=' is not present. That proposal should be a new issue if someone wants to push it.
Yes, that's the problem. I guess it would be easier to keep track of
which fields were set via defaults, and which explicitly. Currently,
that information is lost.

There is a funny thing in 3.6.0a0
>>> '{:<09}'.format(1)
'100000000'
>>> '{:<09}'.format(10)
'100000000'
>>> '{:<09}'.format(100)
'100000000'
>>>
Actually, it behaves like a string, but the format should call internal format function of the passed number and the internal format function should not format different numbers as equal numbers.
Why does it represent number 1 as number 10?
>>> format(1, '<02')
'10'
>>> format(10, '')
'10'
>>>
I guess, there should be a restriction.
Zero padding for numbers should be correct.

You example says to left justify '1'
>>> format(1, '<2')
'1 '
and then pad with '0' instead of ' '.

New changeset de669512df97 by Terry Jan Reedy in branch '2.7':
Issue #15660: Further clarify 0 prefix for width specifier in formats.
https://hg.python.org/cpython/rev/de669512df97
New changeset 34cbc5d8a173 by Terry Jan Reedy in branch '3.5':
Issue #15660: Further clarify 0 prefix for width specifier in formats.
https://hg.python.org/cpython/rev/34cbc5d8a173 

Terry J. Reedy (terry.reedy) wrote:
> You example says to left justify '1'
Nope.
The fill character goes before alignment in the specification (grammatics).
>>> format(1, '0<2')
'10'
>>>
This is right. But 02 - is zero padding of a number which can be done only from the left side.
'<02' means "justify to the left zero padded number"

Terry Reedy wrote:
> If the spec string is still available, it could be searched and the message adjusted if '=' is not present. That proposal should be a new issue if someone wants to push it.
Done now, see Issue 27772.