Mesoporous silica (MS), 3-aminopropyltriethoxysilane (APTES) modified mesoporous silica (AMS), bis(3-trimethoxysilylpropyl)amine modified mesoporous silica (BAMS) and APTES modified solid spherical silica (AS) were prepared and used to immobilize metallocene catalysts for ethylene polymerization. Gel permeation chromatography results showed that polyethylenes (PEs) catalyzed by AMS (or BAMS) supported metallocene catalysts at the molar ratios of Al/Zr = 100, 300 and 500 were of bimodal molecular weight distribution (BMWD); while PEs catalyzed by the above catalysts at the molar ratios of Al/Zr ≥ 800 were of monomodal molecular weight distribution (MMWD). However, MS (or AS) supported metallocene catalysts could only produce PEs with MMWD in spite of the molar ratio of Al/Zr. It was because that AMS (or BAMS) supported catalysts possessed two active sites for ethylene polymerization at low molar ratios of Al/Zr due to the combination effects of mesopore geometrical constraint and amino groups of the supports, which was confirmed by X-ray photoelectron spectroscopy. This brings forward a novel and easy method for the synthesis of polyolefin with BMWD.