Catalytic, reductive C-C bond formation between alkenes and vinyl cyclopropane (VCP) through hydrogen atom transfer (MHAT) is developed. Despite VCP's use as probes in radical-clock experiments, translation of this manifold into synthetic methods for accessing elusive C-C bonds remains largely unexplored. This work represents the first foray into this front where the high chemoselectivity of MHAT for alkene over VCP was pivotal for realizing the strategy. This method exhibits a broad scope, high functional group tolerance, and useful applications.