We modified polyimide (PI) fibers by a novel hydrolysis approach and fabricated PI‐fiber‐reinforced novolac resin (NR) composites with enhanced mechanical properties. We first used an alkaline–solvent mixture containing potassium hydroxide liquor and dimethylacetamide (DMAc) for the surface modification of the PI fibers. The results indicate that the surface roughness and structure of the PI fibers were controlled by the hydrolysis time and the content of DMAc. With the optimized hydrolysis conditions, the tensile modulus of modified PI fibers improved 15% without compromises in the fracture stress, fracture strain, or thermal stability. The interfacial shear strength between the modified PI fibers and NR increased 57%; this indicated a highly enhanced interfacial adhesion. Finally, the tensile and flexural strengths of the composites increased 72 and 53%, respectively. This research provides an effective method for the surface modification of PI fibers and expands their applications for high‐performance composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46595.