A simple chemical solution-based synthesis route has been developed to prepare uniform and shape-controllable Ag3PO4 crystals. Tetrapod- and cube-shaped crystals having a size of about 9–10 μm were prepared from AgNO3 and NH4H2PO4 precursors, and pseudo-octahedral (equiaxial) crystals were prepared from AgNO3 and (NH4)2HPO4. TEM analysis revealed Ag3PO4 crystals to be electron beam sensitive materials, which under a voltage of 200 kV decompose to the metallic Ag, thereby demonstrating the difficulty in determining crystal facets and structural defects using conventional electron diffraction studies. UV–Vis diffuse reflectance spectroscopy was used to study the correlation between structural and optical properties of surfaces of Ag3PO4 crystals. Furthermore, a spatial 3-dimentional (3D) reconstruction of Ag3PO4 surface structures was performed from SEM images. The reconstruction produced realistic 3D mesh models, insomuch that the 3D reconstructed structures provided extra information about the examined crystals. Results suggested that the proposed synthesis route and performed spatial reconstruction of Ag3PO4 had the potential for simulating processing conditions to produce various microcrystals and explore material surface structures and reconstruction of microstructures.