For improving the hydrolytic stability of sulfonated polyimides consisting of five membered anhydrides, novel sulfonated polyimides (NSPIs) were prepared via polymerization of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), with a novel diamine monomer with a pendant sulfonic acid group and 4,4-oxydianiline. Water uptake of this NSPI with an excellent film-forming ability was almost equal to that of Nafion® 117, while their ion exchange capacity (IEC) was 22% higher than Nafion® 117. The loss in weight decreased by 53% and loss in IEC decreased by 66% compared to that of Nafion® 117; both were used to quantitatively measure hydrolytic stability, and radical oxidative stability also increased by 75% when compared with Nafion® 117. Mechanically, this NSPI was superior, and its proton conductivity was higher than Nafion® 117 at elevated temperatures. All these improvements were due to the introduction of this pendant group. Taken together, we herein report a promising renewable energy source based on SPIs capable of displaying proton conductivity and enhanced hydrophilicity.