Abstract: Catalytic hydroamination was proposed as a sustainable solvent-free method for cross-linking two-component silicone mixtures. Cross-linking reactions of amino- and vinyl-containing polysiloxanes were conducted at 120°C in air using titanocene, zirconocene, and hafnocene dichlorides as catalysts. Cross-linking patterns were successfully confirmed by FTIR and solid-state NMR spectroscopies (1H, 13C{1H}, and 29Si). Metallocene catalysts allow obtaining high-quality, colorful silicone rubbers without visible mechanical defects. Catalytic hydroamination shows potential as a sustainable, efficient, and versatile method for silicone cross-linking.