By introducing binary hydroxyl groups into poly(p‐phenylene benzoxazole) (PBO) macromolecular chains, we synthesized dihydroxy poly(p‐phenylene benzobisoxazole) (DHPBO) polymers and then prepared DHPBO fibers by dry‐jet wet‐spinning. Comparative studies were performed between intrinsic PBO fibers and DHPBO fibers. The effects of hydroxyl polar groups on improving the UV aging resistance of PBO fibers were investigated. With the introduction of hydroxyl groups, substantial changes in the chemical structures and surface morphologies of DHPBO fibers were observed. As proved by tensile testing and intrinsic viscosity measurement, the UV resistance of DHPBO fibers is obviously improved compared to that of intrinsic PBO fibers. XRD results indicate that the UV aging of these fibers occurs mainly on the surfaces of fibers. Based on these results, the mechanism of UV aging of PBO fibers was discussed. Copyright © 2009 John Wiley & Sons, Ltd.