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We report a simple and effective nickel-based catalytic system, NiCl2·6H2O/ t BuOK, for the electrophilically activated hydrosilylation of terminal alkenes with primary silanes. This protocol provides excellent performance under mild reaction conditions: exclusive anti-Markovnikov selectivity, broad functional group tolerance (36 examples), and good scalability (TON = 5500). However, the secondary and tertiary silanes are not suitable. Mechanistic studies revealed that this homogeneous catalytic hydrosilylation includes an electrophilically activated Si–H bond process without the generation of nickel hydrides.

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