Traditional dip-assisted layer-by-layer (LbL) assembly produces robust and conformal coatings, but it is time-consuming. Alternatively, spray-assisted layer-by-layer (SA-LbL) assembly has gained interest due to rapid processing resulting from the short adsorption time. However, it is challenging to assemble anisotropic nanomaterials using this spray-based approach. This is because the standard approach for fabricating “all-polyelectrolyte” LbL films does not necessarily give rise to satisfactory film growth when one of the adsorbing components is anisotropic. Here, polymers are combined with a model anisotropic nanomaterial via SA-LbL assembly. Specifically, graphene oxide (GO) is investigated, and the effect of anchor layer, colloidal stability, charge distribution along the carbon framework, and concentration of polymer on the growth and the film quality is examined to gain insight into how to achieve pinhole-free, smooth polymer/GO SA-LbL coatings. This approach might be applicable to other anisotropic nanomaterials such as clays or 2D nanomaterials for future development of uniform coatings by spraying.