Sol-gel-derived organosilica membranes with different linking groups consisting of 2 carbon atoms (ethane, ethylene, and acetylene) were fabricated using bis(triethoxysilyeethane (BTESE), bis(triethoxysilyl)ethylene (BTESEthy), and bis(triethoxysilyl)acetylene (BTESA). No research group has ever proposed tailoring the microstructure and permeation properties of bridged organosilica membranes as a way to control the bond angles. In this study, however, we found that increases in the Si-O-Si and Si-C-C bond angles contributed to the formation of a loose and uniform structure, which was suggested by the blue shift of Si-O-Si and Si-C-C bonds in the FT-IR spectra. BTESA membranes featured a more open and accessible pore structure, which was suitable for the separation of C3H6/C3H8. The present study provides a novel way to design the microstructure and permeation properties of organosilica membranes via controlling the bond angles in the network structure.