In this study, new photonics architectures and aurone-based methacrylic polymers were designed and synthesized for their optical and nonlinear optical properties. The studied polymeric thin films were deposited by spin coating method. SHG and THG effects were measured via Maker fringe technique in transmission mode and determined using theoretical models. Investigations involved the theoretical quantum chemical calculation of dipole moments, frontier molecular orbital HOMO and LUMO energies, and first (β) and second (γ) hyperpolarizabilities. We determined the impact of the substitution in the para position of the phenyl ring and at the dipole moment of the chromophore on the nonlinear optical properties of the investigated polymers. The presented theoretical and experimental studies provide important information with respect to the design of methacrylic-based polymeric thin film devices and supplement existing knowledge with respect to their nonlinear behaviour.