Chemically sprayed fluorine-indium-doped zinc oxide thin films (ZnO:F:In) were deposited on glass substrates. A mixture of zinc pentanedionate, indium sulfate, and fluoride acid was used in the starting solution. The influence of both the dopant concentration in the starting solution and the substrate temperature on the transport, morphological, linear, and nonlinear optical (NLO) properties were fully characterized with atomic force microscopy (AFM), scanning-electron microscopy (SEM), UV-VIS, and photoluminescence (PL) spectroscopies, and the second-harmonic generation (SHG) technique, respectively. A decrease in the resistivity was observed for increasing substrate temperatures, reaching a minimum value of 1.2 × 10−2 Ω cm for samples deposited at 500°C. The surface morphology was also dependent on the dopant concentration in the starting solution and on the substrate temperature. The X-ray diffraction (XRD) patterns revealed that the ZnO:F:In thin solid films are polycrystalline in nature fitting with a hexagonal wurtize type and showing (002) preferential growth for all of the studied samples. The optical transmittance of these films was found to be higher than 80%, from which the optical band gap of these samples was determined. Finally, a clear dependence on the quadratic NLO properties of the developed semiconducting ZnO:F:In thin films with the substrate temperatures was established, where huge x (2)-NLO coefficients on the order of x 33 (2) = 37 pm V−1 were measured for high substrate temperatures.