Simultaneous interpenetrating polymer network silicone hydrogels have been prepared by UV-initiated free radical/cationic hybrid photopolymerization of a mixture of methacrylate macromonomer polyethylene glycol diacrylate (PEGDA) and vinyl ether terminated polydimethylsiloxane macromonomer (VESi). The consumption of each macromonomer upon UV-irradiation was monitored in situ by real-time infrared spectroscopy. The analysis of transmission electron microscope indicated that the silicone hydrogels exhibited a heterogeneous morphology. The physicochemical properties of the silicone hydrogels, such as water content, ion permeability, oxygen permeability, and contact angle were investigated. The results showed that water content and ion permeability increased with the PEGDA content in the formulation, and the silicone hydrogels exhibited excellent oxygen permeability with the highest D (k) of 248 barrer. The results of contact angle measurements indicated that the silicone hydrogels possessed hydrophilic surfaces with the lowest water contact angle of 32A degrees. The study of the protein resistance revealed that the amount of protein adsorbed was significantly reduced with the PEGDA content in the formulation.