Colorless alicyclic polyimides (ALPIs) were synthesized from an alicyclic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BCDA) and an aromatic diamine, 3,4'-oxydianiline (3,4'-ODA). For comparison, a series of crosslinkable ALPI membranes with different content of crosslinkable reagents were prepared. The crosslinkable PI reacts with the crosslinkers and forms covalent bond to create the crosslink structure between PI backbones by free radical reaction. Almost of the crosslinkable PIs exhibit excellent dimensional stability and higher transparency because of the crosslink structure and non-conjugate alicyclic chain. All of the crosslink ALPIs could be coated into flexible and tough films. They had a UV-Vis cut-off at 297 nm and a transmittance of higher than 80% in near ultraviolet region. These PIs show low coefficient of thermal expansion ranging from 57.36 to 47.53 ppm/°C, the glass transition temperature in the range of 336.2-333.0 °C, the decomposition temperature in the range of 433.7-440.0 °C. The crosslinkable ALPIs show excellent optical properties with the excited wavelength ranging from 340 to 328 nm and stronger emission intensity than linear PI, the haze lower than 0.7, the refractive index about 1.6 and the abbe numbers over 165.