The structures of poly(p-phenylenebenzobisthiazole) (PBZT) and poly(p-phenylenebenzobisoxazole) (PBO) fibers have been investigated by fiber diffraction techniques. d-spacings were obtained from equatorial and meridional scans recorded on a four-circle diffractometer. Intensity data were derived from x-ray rotation patterns taken on Weissenberg and vacuum cylindrical cameras. Unit cells were found to be monoclinic and non-primitive, each containing two chains per cell of dimensions a = 11.79(2), b = 3.539(5), c = 12.514(9) A, γ = 94.0(2)o for PBZT; and = 11.20(1), b = 3.540(2), c = 12.050(3) Å, γ = 101.3(1) for PBO. The fiber axes correspond to c. The conformational torsion angle between the bisthiazole and phenylene units and the orientation of chains within the unit cells were obtained from a ‘linked-atom least-squares’ (LALS)refinement procedure. A packing model is proposed for each polymer in which two independent molecular chains are displaced longitudinally by discrete rather than random increments. Primitive unit cells (Z = 1), besides requiring perfect axial registry of molecular chains, suffer from the occurrence of short intermolecular contacts and are rejected from further consideration.