We applied photoemission tomography (PT) to a unique one-dimensional row structure of a picene multilayer realized on an anisotropic Ag(110) surface. Taking advantage of the simplified structure of the multilayer film, we successfully deconvoluted the photoelectron momentum maps of three frontier orbitals of picene. Thereafter, the clearly deconvoluted experimental momentum maps were compared to the Fourier transform simulation of the molecular orbitals of picene in detail, enabling not only the evaluation of the electronic structure of the picene in the multilayer but also the determination of the molecular orientation in the multilayer within a few degrees. In addition, the PT results indicated the orientation of the molecules in all layers to be flat-lying. The successful demonstration of PT of the multilayer molecular film marks an important step toward the wide-range utilization of the PT technique.