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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...'''
1x01 - Pilot* 1x16 - Shadow* 2x03 - Bloodlust (x2)* 3x09 - Malleus Maleficarum* 3x11 - Mystery Spot* 4x01 - Lazarus Rising* 4x02 - Are You There, God? It's Me, Dean Winchester (x2)* 4x06 - Yellow Fever (x2)* 4x10 - Heaven and Hell* 4x16 - On the Head of a Pin* 5x15 - Dead Men Don't Wear Plaid* 6x09 - Clap Your Hands if You Believe* 6x11 - Appointment in Samarra* 7x03 - The Girl Next Door (x2)* 7x04 - Defending Your Life (x4)* 8x01 - We Need to Talk About Kevin* 9x17 - Mother's Little Helper (x3)* 9x18 - Meta Fiction (x2)* 10x03 - Soul Survivor (x2)* 10x15 - The Things They Carried* 10x23 - Brother's Keeper * 11x17 - Red Meat
'''Sam drives the Impala with Dean as a passenger in...'''
1x02 - Wendigo* 1x08 - Bugs (x3)* 1x11 - Scarecrow* 1x12 - Faith* 1x13 - Route 666* 1x19 - Provenance* 1x20 - Dead Man's Blood* 1x22 - Devil's Trap* 2x01 - In My Time of Dying* 3x02 - The Kids are All Right* 4x02 - Are You There, God? It's Me, Dean Winchester* 4x06 - Yellow Fever* 4x16 - On the Head of a Pin* 5x05 - Fallen Idols* 7x03 - The Girl Next Door* 9x05 - Dog Dean Afternoon* 9x23 - Do You Believe in Miracles?* 10x02 - Reichenbach* 10x12 - About a Boy* 10x16 - Paint it Black
'''Sam drives the Impala with another passenger in...'''
1x22 - Devil's Trap (John)* 2x01 - In My Time of Dying (John)* 3x02 - The Kids are All Right (Ben)* 4x08 - Wishful Thinking (Wes Mondale)* 4x09 - I Know What You Did Last Summer (Ruby 1.5)* 6x22 - The Man Who Knew Too Much (Robin)* 10x20 - Angel Heart ( Cas)* 11x21 - All in the Family ( Cas, Donatello)* 11x23 - Alpha and Omega ( Cas, Crowley , Rowena)