Combining hydrophobic materials such as polydimethylsiloxane (PDMS), a natural hydrophobic material with typical hydrophilic monomers without using organic solvent remains a big challenge due to their extreme different properties; hence, fabricating a class of silicone hydrogels with two extremes without use of organic solvents could bring us a novel class of silicone hydrogels. Herein, a range of PDMS-HEMA-PEGMA hydrogels was prepared from hydroxyl-terminated PDMS, 2hydroxyethylmethacrylate (HEMA), poly (ethylene glycol) methacrylate (PEGMA), and isophorone diisocyanate via condensation and radical copolymerization reactions.The infrared results confirmed the PDMS-HEMA-PEGMA network formation, while the hydrophilicity of the as-prepared block copolymer was dependent on (PDMS-HEMA)/PEGMA ratio. Increasing the PEGMA content resulted in increased equilibrium water content, phase separation, surface roughness, and tensile strength, while the tensile modulus, elongation at break, optical transmittance, water contact angle, and oxygen permeability (Dk) were decreasing. At PEGMA content of 28.3%, the relative protein adsorption ratio decreased to 20% and 36% for bovine serum albumin and lysozyme, respectively, compared with that of the control (PDMS-HEMA), suggesting antiprotein adsorption ability. In overall, the results showed that the PDMS-HEMA-PEGMA hydrogels not only exhibited remarkable hydrophilicity and suppressed protein adsorption but also maintained higher optical transparency and oxygen permeability (Dk).