A theoretical study was elaborated to support the experimental results of the Zn-doped α-AgWO. Theses α-AgZnWO (0 ≤ x ≤ 0.25) solid solutions were obtained by coprecipitation method. X-ray diffraction data indicated that all α-AgZnWO (0 ≤ x ≤ 0.25) microcrystals presented an orthorhombic structure. The experimental values of the micro-Raman frequencies were in reasonable agreement with both previously reported and calculated results. Microscopy images showed that the replacement of Ag by Zn promoted a reduction in the average crystal size and modifications in the morphology, from rod-like with hexagonal shape to roll-like with a curved surface. A theoretical methodology based on the surfaces calculations and Wulff constructions was applied to study the particle shapes transformations and the surface energy variations in α-AgZnWO (0 ≤ x ≤ 0.25) system. The decrease in the band gap value (from 3.18 to 3.08 eV) and the red shift in photoluminescence with the Zn addition were associated with intermediary energy levels between the valence and conduction bands. First-principles calculations with density functional theory associated with B3LYP hybrid functional were conducted. The calculated band structures revealed an indirect band gap for the α-AgZnWO models. The electronic properties of α-AgWO and α-AgZnWO microcrystals were linked to distortion effects and oxygen vacancies (V) present in the clusters, respectively. Finally, photoluminescence properties of α-AgWO and α-AgZnWO microcrystals were explained by means of distortional effects and oxygen vacancies (V) in [AgO] (y = 2, 4, 6, and 7) and [WO] clusters, respectively, causing a red shift. Calculations revealed that the substitution for Ag with Zn occurred randomly in the α-AgWO lattice, and it was more favorable on the Ag4 site, where the local coordination of Ag cations was four.