cis- and trans-Isomers of the platinum(II) nitrile complexes [PtCl₂(NCR)₂] (R = NMe₂, N(C₅H₁₀), Ph, CH₂Ph) were examined as catalysts for hydrosilylation cross-linking of vinyl-terminated polydimethylsiloxane and trimethylsilyl-terminated poly(dimethylsiloxane-co-ethylhydrosiloxane) producing high quality silicone rubbers. Among the tested platinum species the cis-complexes are much more active catalysts than their trans-congeners and for all studied platinum complexes cis-[PtCl₂(NCCH₂Ph)₂] exhibits the best catalytic activity (room temperature, c = 1.0 × 10⁻⁴ mol/L, τ_pot-life 60 min, τ_curing 6 h). Although cis-[PtCl₂(NCCH₂Ph)₂] is less active than the widely used Karstedt’s catalyst, its application for the cross-linking can be performed not only at room temperature (c = 1.0 × 10⁻⁴ mol/L), but also, more efficiently, at 80 °C (c = 1.0 × 10⁻⁴–1.0 × 10⁻⁵ mol/L) and it prevents adherence of the formed silicone rubbers to equipment. The usage of the cis- and trans-[PtCl₂(NCR)₂] complexes as the hydrosilylation catalysts do not require any inhibitors and, moreover, the complexes and their mixtures with vinyl- and trimethylsilyl terminated polysiloxanes are shelf-stable in air. Tested catalysts do not form colloid platinum particles after the cross-linking.