Two phosphates, Cs2Zn5(PO4)4 and Cs3La(PO4)2 have been successfully synthesized by employing the conventional solid‐state reaction method, and their structures were determined by single‐crystal X‐ray diffraction. Cs2Zn5(PO4)4 owns a three‐dimensional ∞3[Zn4P4O16] framework and Cs3La(PO4)2 features ∞2[La3P6O29] layers spreading in the bc plane. Infrared spectroscopy, UV/Vis‐NIR diffuse reflectance spectroscopy were performed. The thermal properties and electronic structures of two compounds were investigated. In addition, the Ce3+ doped Cs3La(PO4)2 phosphor was synthesized and its photoluminescence was analyzed. The results indicate that the Cs2Zn5(PO4)4:0.01Ce3+ phosphor can be excited by ultraviolet light to obtain blue luminescence.