Highly active catalysts composed of titanocene complexes and nanometric sodium hydride have been developed for the hydrogenation of styrene under normal pressure. The highest initial catalytic activity reached 138 s(-1) (average value in the first 1 min), which is higher than previously reported data for the hydrogenation of styrene. The highest number of catalytic turnover reached 21,700 in 2 h. An effect of steric hindrance of substituents of titanocene complexes on the catalytic efficiency was observed.