To improve the paper properties of the poly(1,3,4-oxadiazoles) (POD), the POD pulps were prepared by prechemical and mechanical methods to increase their polarity, contact area, and interaction. The fibrillated degree of the staple fibers was evaluated by the Canadian Standard Freeness and the specific surface area, while the surface free energy was calculated by the Micro–wilhelmy method. Meanwhile, the functional groups and compositions on the surface of the POD fibers were confirmed by the FTIR–ATR and the X-ray photoelectron spectroscopy, and the surface morphological structure and the crystalline structure of the POD fibers were observed by the fiber analyzer, scanning electron microscope, and Wide-angle X-ray diffraction, respectively. It was found that the pronounced abrasive and distinctive grooves were formed on the surface of the POD fibers after prechemical and mechanical treatment. The surface free energy of POD fibers increased 8.41%, and the polar part increased by 32.10% after treatment. It was confirmed that the polar functional groups and fibril were formed after chemical and mechanical treatment, so the interaction of the POD fibers was highly enhanced, and as a result the apparent density, tensile strength, fold endurance, and tear strength of the paper formed by those treated fibers were all improved apparently. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39818.