Herein, we present the rare-earth (RE) activated Ca_0.5Y_1−x(WO₄)₂:xEu³⁺ phosphors prepared using a surfactant-assisted hydrothermal route. From the synthesized powder samples of Ca_0.5Y_1−x(WO₄)₂:xEu³⁺, nanosized, thin phosphor films were fabricated based on the pulsed laser deposition (PLD). Structural studies suggest that Ca_0.5Y_1−x(WO₄)₂ doped with Eu³⁺ belongs to the scheelite tetragonal crystal structure. The powder phosphors show signs of bi-pyramid-like micro-architectures. The down-conversion luminescence studies suggest the presence of a predominant transition attributed to the red color in the visible region. The Judd–Ofelt theory has been incorporated to estimate the photophysical parameters and luminescence quantum efficiencies of both Ca_0.5Y_1−x(WO₄)₂:xEu³⁺ powder and thin film phosphors. The color chromaticity coordinates and luminescence decay times were estimated. The effect of alkali compounds on the prepared powder phosphors was investigated. The results indicate that both the powder and thin film phosphors are the best candidates for display and electro/cathodo-luminescence applications.