B(C6F5)3 catalyzed hydrosilylation of 1,2-polybutadienes has been developed. A wide variety of hydrosilanes substituted with aryl and alkyl groups form Anti-Markovnikov's product with 1,2 – Polybutadienes. 1,4- Polybutadienes with internal double bonds show good reactivity with the present catalytic system, which are otherwise found to be less reactive towards the transition metal catalysts. The silanes with bulky groups such as diphenyl and triphenyl have efficiently been hydrosilylated at room temperature using this methodology. Silyl-substituted polymer products were characterized by 1H, 13C, 29Si NMR and GPC techniques.