The band edges of metal-halide perovskites with a general chemical structure of ABX (A, usually a monovalent organic cation; B, a divalent cation; and X, a halide anion) are constructed mainly of the orbitals from B and X sites. Hence, the structural and compositional varieties of the inorganic B-X framework are primarily responsible for regulating their electronic properties, whereas A-site cations are thought to only help stabilize the lattice and not to directly contribute to near-edge states. We report a π-conjugation-induced extension of electronic states of A-site cations that affects perovskite frontier orbitals. The π-conjugated pyrene-containing A-site cations electronically contribute to the surface band edges and influence the carrier dynamics, with a properly tailored intercalation distance between layers of the inorganic framework. The ethylammonium pyrene increased hole mobilities, improved power conversion efficiencies relative to that of a reference perovskite, and enhanced device stability.