In the present work, we have investigated the electrical, linear, and nonlinear optical parameters of thiophene-centering chalcone doped PMMA thin films. Using a standard spray pyrolysis technique, (E)− 1-(thiophen-2-yl)− 3–3(3,4,5-trimethonyl) prop-2-en-1-one blended PMMA thin films were deposited for different chalcone concentrations (10%, 30%, and 50% wt.). With the advent of FESEM analysis, the uniform and consistent behavior of the deposited thin film was verified. The optical band gap is found to diverge from 3.83 to 3.77 eV with concentration using UV–visible spectroscopy, and photoluminescence studies show that material emits in the blue band region. The deposited thin films show nonlinear absorption coefficients (β) and third-order nonlinear optical susceptibility Imχ(3) in the order of 10−4 cm/W and 10−7 e.s.u., respectively. I-V curves revealed that the electrical conductivity of chalcone doped PMMA thin films ranges from 1.78 to2.39μS/cm. Non-linear optical findings of deposited thin films are recommended for optoelectronic device applications.