On paper it predates it but Java was "industrial development ready" from day 1. Python 1 was barely used and it was more of an academic toy of sorts, it took Python 2 to come on the scene for Python to even be mentioned in the same sentence as Java.
I don't know the exact chronology of CLASSPATH versus PYTHONPATH, but I can tell you that CLASSPATH usage is pervasive and has been so from the start, for Java (I was using Maven 2 in 2007 and even then CLASSPATH was established, being also used by the Ant and Eclipse and other, older, tools), while PYTHONPATH is definitely not used to the same effect in Python, it's an afterthought.