Tailored polymer materials exhibiting high-glass transition temperatures, cross-linked matrices, and/or strong intermolecular interactions containing electric-field poled nonlinear optical (NLO) chromophores are promising materials for applications in optical telecommunication, high-performance computing, and data transmission. Although the current design parameters have led to significant advances in NLO materials, we introduce an alternative, yet highly effective, approach in which a NLO chromophore is cocrystallized with a polymer, forming a noncentrosymmetric hybrid host-guest complex. Specifically, poly(ethylene oxide) (PEO) and 2-chloro-4-nitroaniline (CNA) will cocrystallize and exhibit second harmonic generation (SHG) activity due to the formation of a noncentrosymmetric cocrystalline unit cell where the chromophore exhibits acentric alignment. Furthermore, the hybrid PEO/CNA films exhibit interesting SHG activity at elevated temperature in which SHG intensity decreases to zero when the cocrystal orientation randomizes due to sample melting. Aligning and maintaining a cocrystalline domain orientation via the formation of hybrid host-guest complexes, while imparting SHG properties, is an innovative approach for creating materials exhibiting SHG properties.