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Alkenes are an important class of organic molecules found among synthetic intermediates and bioactive compounds. They are commonly synthesized through stoichiometric Wittig‐type olefination of carbonyls and imines, using ylides or their equivalents. Despite the importance of Wittig‐type olefination reactions, their catalytic variants remain underdeveloped. We explored the use of transition metal catalysis to form ylide equivalents from readily available starting materials. Our investigation led to a new copper‐catalyzed olefination of imines with alkenyl boronate esters as coupling partners. We identified a heterobimetallic complex, obtained by hydrocupration of the alkenyl boronate esters, as the key catalytic intermediate that serves as an ylide equivalent. The high E‐selectivity observed in the reaction is due to the stereoselective addition of this intermediate to an imine, followed by stereospecific anti‐elimination. [ABSTRACT FROM AUTHOR]