Organic semiconductor applications will significantly benefit from atomically precise, cofacial stacking of extended pi-conjugated molecular systems for efficient charge transport. Surface-assisted self-assembly of poly(hetero)cyclic molecules via donor-acceptor type pi-pi stacking is a promising strategy to organize functional, many-layered architectures. We have employed tris(N-phenyltriazole) as a model system to achieve molecular-level structural ordering through more than 20 molecular layers from its own metal-templated monolayer. Effective charge transport through such layers enabled molecular-resolution imaging by scanning tunneling microscopy. The structure and chemical composition of the films, grown on Ag(111) or Au(100), were further analyzed by noncontact atomic force microscopy and X-ray photoelectron spectroscopy, revealing a cofacial stacking geometry of the molecular layers. Scanning tunneling spectroscopy measurements show a decrease of the band gap with increasing film thickness, consistent with pi-pi stacking and electron delocalization. The present study provides new strategies for the fabrication of normally inaccessible structural motifs, atomic precision in organic films, and the effective conduction of electrons through multiple organic molecular stacks.