In this communication, we present the syntheses, structure, infrared (IR) spectroscopic, and electronic transport properties for two new Perylene-containing donor-acceptor complexes, Perylene-pDNB (1) and Perylene-TCNP (2). The 2:1 complex with pDNB, complex 1, crystallizes in the triclinic space group P " 1 with cell dimensions a = 7.7488(12) Å , b = 9.7125(15) Å , c = 10.6864(17) Å , a = 80.829(7)°, b = 84.893 (7)°and c = 89.495(6)°, while complex 2, the 1:1 complex with TCNP, crystallizes in the orthorhombic space group Cmca with a = 18.264(4) Å , b = 7.405(2) Å and c = 14.674(3) Å . Structural features of the constituent donor and acceptor molecules were compared to those for the free components and, when coupled with IR spectroscopic measurements, suggested that both complexes contained neutral components. This conclusion was further supported by electronic transport measurements that revealed both complexes to be insulators. Graphical Abstract Herein we present the structure and both the IR spectroscopic and transport properties for new