3.1 is much simpler than 2.5 or 2.6, but currently there is a serious lack of third-party add-ins that support its environments (large applications that use it for scripting, etc.), and tools like the IDE. So, a lot depends on what you want to learn Python - if only for personal edification, 3.1 is perfect; if he actually creates or controls applications, websites, etc., then 2.5 or 2.6 will serve you better at the present time (he 3.*will undoubtedly reach and surpass 2.*in the future, but the future is not here yet; -.)
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