As a new kind of functionalized polysiloxane with chemical reactivity, bio-phenol polysiloxane was synthesized through facile heterogeneous catalytic route. Bio-phenol polysiloxane/polycarbonate (Si/PC) block copolymer was synthesized via a three-step approach, and the effect of the amount of bio-phenol polysiloxane on the properties of Si/PC copolymer was then studied. The structure and morphology of Si/PC copolymer were characterized, showing that, when the amount of bio-phenol polysiloxane reached 20%, the pyrolysis temperature of Si/PC copolymer at 5% weight loss was 450.8 °C which was 76.1 °C higher than pure PC. The oxygen permeability of 20%Si/PC copolymer membrane was 502.65 cm3/m2·24h·0.1MPa, which was increased by 128.4% compared with pure PC membrane. The mechanical property and hydrophobicity of Si/PC copolymer had been improved.