Changes in crystal strain and crystallite orientation of three varieties of PBO fibre (namely PBO AS, HM and HM+) have been investigated during deformation from the analysis of diffraction patterns obtained across single filaments, using a synchrotron X-ray source. Crystal strain was measured from the positions of the meridional reflections and orientation calculated from azimuthal broadening of the equatorial reflections. It has been demonstrated that no difference in crystal strain across the fibre exists, with the calculated strain being equal between fibre skin and core at a given level of stress. Further skin-core crystallite orientation analysis (calculation of the orientation parameter \(\left\langle {\sin ^2 \theta } \right\rangle\)) proved that the AS fibre was the only PBO variety with a significant difference in orientation across the fibre, with the core region being less oriented due to the processing conditions. The skin and core orientation of all three fibres was found to improve with deformation, with the core of the AS fibre showing a significantly higher rate of improvement. This resulted in a similar level of orientation for both skin and core regions of the PBO AS fibre at high levels of stress. The fibre modulus was found to increase with the increasing initial degree of crystallite orientation. Furthermore, improvement in orientation with external stress was related to \(\left\langle {\sin ^2 \theta } \right\rangle\)σ = 0, with higher values resulting in greater shear forces on the crystallites and therefore a greater rate of orientation improvement.