To explore the coordination possibilities of perylene-based ligands with a larger conjugated π-system, four Zn^II, Mn^II, and Co^II coordination polymers with perylene-3,4,9,10-tetracarboxylate (ptc) and the chelating 1,10-phenanthroline (phen) ligands were synthesized and characterized: {[Zn₂(ptc)(phen)₂](H₂O)₁₀}_∞ (1), {[Zn₃(ptc)(OH)₂(phen)₂](H₂O)₃}_∞ (2), {[Mn(ptc)_0.5(phen)(H₂O)₂](H₂O)_1.5}_∞ (3), and {[Co(ptc)_0.5(phen)(H₂O)₂](H₂O)_2.5}_∞ (4). Structural analysis reveals that complexes 1 and 2 both take one-dimensional polymeric chain structures with dinuclear and trinuclear units as nodes, respectively, which are further extended via the accessorial secondary interchain interactions, such as C–H···O H-bonding or aromatic π···π stacking interactions, to give rise to the relevant higher-dimensional frameworks. Compound 3 has a two-dimensional sheet structure that is further assembled to form a three-dimensional framework by interlayer π···π stacking interactions. Complex 4 is a one-dimensional ribbon-like array structure that is interlinked by the co-effects of intermolecular π···π stacking and C–H···π supramolecular interactions, resulting in a higher-dimensional framework from the different crystallographic directions. Moreover, complexes 1–4 exhibit strong solid-state luminescence emissions at room temperature, which mainly originate from intraligand π→π* transitions of ptc.