An intermolecular, three-component reductive dicarbofunctionalization of alkenes is presented here. The combination of Ni catalysis with TDAE as final reductant enables the direct formation of Csp(3)-Csp(3) and Csp(3)-Csp(2) bonds across a variety of pi-systems using two different electrophiles that are sequentially activated with exquisite selectivity under mild reaction conditions.