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Baby is without a doubt Dean's car, but Sam does his share of driving the Impala as well.
[http://samdrives.livejournal.com/ samdrives] catalogs all known instances of Sam driving the Impala. Additionally, it notes when Sam drives a car other than the Impala, as well as when the Impala is driven by other people besides Sam or Dean. The compilation is complete through
the first half of season 12, and includes screenshots, approximate timestamps, and season-by-season [http://samdrives.livejournal.com/tag/summary summaries].
'''Sam drives the Impala on his own (without any passengers) in...'''
* 10x23 - Brother's Keeper
* 11x17 - Red Meat