The high performance of poly p-phenylene-2,6-benzobisoxazole (PBO) fibre in mechanical properties and environmental resistance provides great potential applications as reinforcement fibres for composites. However, poor adhesion between PBO fibre and matrix is found because of the chemically inactive and/or relatively smooth surface of the reinforcement fibre. Here, we report the surface modification of PBO fibres by O2 and NH3 plasma treatments. The surface energy and roughness are increased for both sized and extracted fibres after plasma treatments. The sized fibre shows marginal improvement in interfacial adhesion and no change in fibre tensile strength because of the barrier effect of the sizing layer. For the extracted fibre, the plasma treatments cause reduction in both interfacial adhesion and the tensile strength, which is sensitive to plasma treatment conditions as revealed by a bimodal Weibull statistical distribution analysis. The fibre surface roughness is increased and more surface flaws are induced, which could result in coarse interface structures when the treated fibre surface has no adequate wetting and functional groups.