In the present work, AgCl microcrystals were obtained by solvothermal crystallization to investigate the effect of H+, Na+, K+, and different shape-tailoring agents (non-ionic: polyvinylpyrrolidone vs. anionic: sodium dodecyl sulfate) on the textural and photocatalytic properties of the samples. The crystallization process resulted in secondary products, such as AgxO or Ag, AgClO3, AgClO4, which were further transformed during the photocatalytic tests. The most efficient photocatalyst (assessed for methyl orange degradation) was synthesized using HCl, as a chloride source and polyvinylpyrrolidone, as a shape-tailoring agent. Therefore, the ability of polyvinylpyrrolidone to enhance the photocatalytic activity was also investigated, and it was found that the addition of 0.6 g polyvinylpyrrolidone resulted in the most efficient photocatalyst. Moreover, AgxO, being a charge separator, could play a critical role in the photocatalytic process, while reversibly transforming to Ag back and forth.