Eight platinum acetylide complexes have been synthesized and characterized. The catalytic properties of these complexes in curing silicone rubber by hydrosilylation have been tested. Among the complexes tested, trans‐Pt(PPh3)2[―C≡CC(CH3)2OSi(CH3)3] 2 (2), trans‐Pt(PPh3)2[―C≡CC(CH3)2OSi(CH2CH3)3]2 (3), trans‐Pt(PPh3)2[―C≡CC(CH3)2OSiPh(CH3)2]2 (4), trans‐Pt(PPh3)2[―C≡C(C6H10)OSi(CH3)3]2 (6), trans‐Pt(PPh3)2[―C≡C(C6H10)OSi(CH2CH3)3]2 (7), and trans‐Pt(PPh3)2[―C≡C(C6H10)OSiPh(CH3)2]2 (8) exhibited sufficiently long pot‐lives (15 days) at room temperature and short silicone rubber curing times of 10–35 min at 100°C or 1–5 min at 120°C. Copyright © 2012 John Wiley & Sons, Ltd.