We have developed a palladium‐catalyzed regioselective and enantiospecific ring‐opening Suzuki–Miyaura arylative cross‐coupling of N‐tosyl‐2‐arylazetidines to give enantioenriched 3,3‐diarylpropylamines. This reaction represents an example of transition‐metal‐catalyzed ring‐opening cross‐coupling using azetidines as a non‐classical alkyl electrophile. Density functional theory rationalized the mechanism of the full catalytic cycle, which consists of the selectivity‐determining ring opening of the azetidine, reaction with water, rate‐determining transmetalation, and reductive elimination. Transition states of the selectivity‐determining ring‐opening step were systematically determined by the multi‐component artificial force induced reaction (MC‐AFIR) method to explain the regioselectivity of the reaction.