Polymer-coated particles were used to develop a novel catalyst technology for the production of broad/bimodal polyethylene in a single reactor. The methods for broad/bimodal polyethylene by catalyst technology, such as hybrid catalyst, composite support, and diffusion control, were combined together in this catalyst technology. An improved phase inversion method was used to fabricate poly[styrene-co-(acrylic acid)] (PSA) coated silica particles (SiO2/PSA). Core shell structure was obviously observed in the resulting SiO2/PSA. SiO2/PSA showed a significant barrier effect to the diffusion of 1-hexene and hexane but but no barrier effect to the diffusion of ethylene. This means the PSA layer has a selective barrier effect to the diffusion of small molecules. PSA-coated silica particles were used to support (n-BuCp)(2)ZrCl2/TiCl4, TiCl3/TiCl4, and Cp2ZrCl2/Fe based hybrid catalysts. The ethylene polymerization results indicated that the two different active sites can perform independently, and broad/bimodal polyethylene was obtained by all hybrid catalysts. The polydispersity index of the resulting polyethylene was as high as 18.13, even 44.5. The style of the activity profile was determined by whether the active sites in the core needed a cocatalyst or not.