Hydrosilylation of C-C double and C-C triple bonds is one of the most widely used processes in organosilicon chemistry, mostly catalyzed by Pt-based complexes. We report here the synthesis of an air-stable dicationic Zn2+-based complex in a hemilabile tris(2-methyl-6-pyridylmethyl) phosphine (TmPPh) ligand,12+[B(C6F5)4]2. When heated,12+[B(C6F5)4]2activates Si-H bonds reversiblyvialigand/metal cooperation between Lewis acidic Zn2+and Lewis basic N centers in a frustrated Lewis pair (FLP) type fashion. Consequently,12+[B(C6F5)4]2was found to be an effective catalyst for hydrosilylation reactions of C-C double and C-C triple bonds. Remarkably, these hydrosilylation reactions can be loaded under aerobic conditions, as well as, in some cases, work under neat conditions. The mechanism of the activation of the Si-H bond and the hydrosilylation reaction is proposed based on experiments and density functional theory (DFT) calculations.