Proton exchange membranes (PEMs) are a key component of a proton exchange membrane fuel cell. Sulfonated polyimides (SPIs) were doped by protic ionic liquid (PIL) to prepare composite PEMs with substantially improved conductivity. SPIs were synthesized from diamine, 2,2-bis[4-(4-amino-phenoxy)phenyl]propane (BAPP), sulfonated diamine, 4,4'-diamino diphenyl ether-2,2'-disulfonic acid (ODADS) and aromatic anhydride. BAPP improved the mechanical and thermal properties of SPIs, while ODADS enhanced conductivity. A PIL, 1-vinylimidazolium trifluoromethane-sulfonate ([VIm][OTf]), was utilized. [VIm][OTf] offered better conductivity, which can be attributed to its vinyl chemical structure attached to an imidazolium ring that contributed to ionomer-PIL interactions. We prepared sulfonated polyimide/ionic liquid (SPI/IL) composite PEMs using 50 wt% [VIm][OTf] with a conductivity of 7.17 mS/cm at 100 °C, and in an anhydrous condition, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (DSDA) was used in the synthesis of SPIs, leading to several hundred-times improvement in conductivity compared to pristine SPIs.