Ag3PO4 microparticles (MPs) were prepared through a facile chemical precipitation route and using silver acetate (AgAc) as metal salt. The effect of annealing temperature (Ta) and time (τa) on the actual photocatalytic (PC) activity of Ag3PO4 MPs is investigated. The optimal annealing parameters are Ta of 400 °C and τa of 90 min. The enhanced PC activity by annealing at 400 °C is ascribed to the increase of electron mobility. Besides, an Ag3PO4 photoelectrode was fabricated through a drop-coating deposition route, which demonstrates a photocurrent density of 80 μA/cm2 and ac-ceptable stability. The n-type conduction behavior of Ag3PO4 is verified by a Mott-Schottky (M-S) plot.