Bi(1.5-x)Zn(0.92-y)Nb(1.5)O(6.92-δ) thin films have the potential to be implemented in microwave devices. This work aims to establish the effect of the substrate and of the grain size on the optical and dielectric properties. Bi(1.5-x)Zn(0.92-y)Nb(1.5)O(6.92-δ) thin films were grown at 700 °C via pulsed-laser deposition on R-plane sapphire and (100)(pc) LaAlO(3) substrates at various oxygen pressures (30, 50, and 70 Pa). The structure, morphology, dielectric and optical properties were investigated. Despite bismuth and zinc deficiencies, with respect to the Bi(1.5)Zn(0.92)Nb(1.5)O(6.92) stoichiometry, the films show the expected cubic pyrochlore structure with a (100) epitaxial-like growth. Different morphologies and related optical and dielectric properties were achieved, depending on the substrate and the oxygen pressure. In contrast to thin films grown on (100)(pc) LaAlO(3), the films deposited on R-plane sapphire are characterized by a graded refractive index along the layer thickness. The refractive index (n) at 630 nm and the relative permittivity (ε(r)) measured at 10 GHz increase with the grain size: on sapphire, n varies from 2.29 to 2.39 and ε(r) varies from 85 to 135, when the grain size increases from 37 nm to 77 nm. On the basis of this trend, visible ellipsometry can be used to probe the characteristics in the microwave range quickly, nondestructively, and at a low cost.