Nickel modified Titanium silicalite 1 (TS-1) catalysts provided an environmentally benign and effective method for butadiene epoxidation. Certain loading of modified Ni in our system significantly promoted TS-1 catalytic activity. The product vinyloxirane (VO) was obtained with high yield of 0.49 mol/L (theoretic equilibrium value 0.52 mol/L). The turnover number (TON, determined as the molar VO obtained per molar Ti atom) reached 1,140. Besides, the catalyst kept high activity during five runs of reusability test. XRD, N-2 adsorption and desorption, TPR, XPS, FT-IR and DR UV-Vis were employed to characterize the specific Ni role to Ti-site in Ni/TS-1 catalysts. Titanium silicalite 1 (TS-1) modified with different nickel contents as catalysts for the epoxidation of butadiene (BD) with hydrogen peroxide (H2O2). Vinyloxirane (VO) was obtained with high yield TON.