In http://docs.python.org/dev/library/struct.html,

it says
"Native byte order is big-endian or little-endian, depending on the host 
system. For example, Motorola and Sun processors are big-endian; Intel 
and DEC processors are little-endian."

This is a gross over-generalization at best.  Off the top of my head, 
current Linux kernels run the Intel Itanium in big-endian mode. (Though, 
I don't recall if there's a non-privileged instruction to flip 
endianness, system headers and system calls are defined in big-endian 
order, which is what's most relevant to the struct module.)  Sun SPARC 
v9 is bi-endian. Intel Itanium and XScale processors are bi-endian.  Dec 
Alphas are bi-endian.  (Though, I'm only aware of Cray using Alphas in 
big-endian mode.)

The quoted paragraph should name specific processors which are single-
endian (Intel Core 2, Sun SPARC v8) and/or provide a Wikipedia 
reference, rather than making incorrect statements.

Intel Itanium machines running Linux are probably the most common 
systems where this statement's inaccuracy is likely to cause confusion 
among developers.