We discuss features of the surface morphology and molecular ordering of Langmuir-Blodgett (LB) films from complexes of poly(naphthoylene benzimidazole) precursor and stearic acid. The anisotropic shape of the rigid ladder polymers with conjugated backbones promotes high in-plane ordering of the macromolecules during formation of LB films. Atomic force microscopy, complemented by X-ray measurements, was used for characterization of the molecular ordering and surface morphology of LB films on a wide range of scales. The surfaces of these LB films are very smooth, with microroughness of 0.3-0.6 nm for films consisting of four or five layers. On the molecular scale we observe wavy ridges aligned along the dipping direction, which corresponds to the direction of the macromolecular backbones. The changes in surface morphology and rearrangement of the molecular backbones associated with thermal cyclization are discussed.