A new type of salt-stabilized solid silylzinc pivalates prepared from the silyllithium reagents via transmetalation with Zn(OPiv)₂ is reported. These silylzinc pivalates showed enhanced air and moisture stability and unique reactivity in the nickel-catalyzed regioselective alkyl and benzylsilylation of alkenes. Kinetic experiments highlighted the crucial involvement of OPiv-coordination in improving the reactivity of silylzinc pivalates.