SiO2-supported silyl chromate catalyst (UCC S-2 catalyst) is an important catalyst for the commercial production of polyethylene. Cann first reported a possible green synthesis route for the preparation of S-2 catalyst through transformation from Phillips catalyst by addition of triphenylsilanol (TPS) to avoid the use of toxic bis(triphenylsilyl) chromate (BC). In this work, this green synthesis route was further investigated by the combination of experimental and theoretical methods. The obtained catalyst was named as PS catalyst based on the incomplete conversion of Phillips catalyst to S-2 catalyst. Polymerization activity of PS1.5 catalyst was higher than that of S-2 catalyst with either TEA or MAO as cocatalyst. The existence of the simultaneously formed hydroxyl group and its coordination to the reduced Cr site was favorable to the PS catalyst, and this might attribute to the higher polymerization activity of PS catalyst than that of 5-2 catalyst. A further modification of PS catalyst by a series of alkyl chlorosilane compounds showed that the role of the electron-withdrawing group only limited at a certain distance away from Cr active site. This preliminary study provided a solid basis for a further innovation of PS catalysts and final substitution of S-2 catalyst in commercial processes. (C) 2010 Elsevier B.V. All rights reserved.