Three-dimensionally ordered macroporous polyethylenes (3DOM PE) with pore size ranging from 135 nm to 410 nm were prepared using supported catalysts on the surface of silica microsphere as template, followed infiltration of gaseous ethylene and polymerization. The morphology of 3DOM PE was characterized by SEM and the reflectance spectrum was recorded by UV-vis. It is shown that the pores are uniform, flexible and arranged in a highly ordered fashion. Reflectance spectrum of 3DOM PE also provided verification of the uniform nature of the Sample. Moreover, the effect of confined space on polymerization was investigated by GPC and DSC. The results indicate that the porous PE possesses higher M. compared with bulk PE, and exhibits lower melting temperature and crystallinity than those of bulk PE. (C) 2008 Elsevier Ltd. All rights reserved.