The luminescence properties of Ce:LuPO4 depend on both the Ce3+ center and the host lattice. In this article, we studied the dependence of the luminescence properties of Ce:LuPO4 on both the doping concentration of Ce3+ and the size and morphology of the LuPO4 matrix at micro- and nanosize regimes. The crystalline behavior of Ce:LuPO4, including its size: and shape, was investigated via precursor transformation crystallization. On the basis of this crystallization approach, Ce:LuPO4 hollow nanosphereS, nanorods, and regular tetrahedrons were obtained. For micro- and nano structured Ce:LuPO4, the surface-induced chemical bonding architecture can be effectively varied by controlling the size of the crystalline material and: its geometry. Our experimental observations demonstrate that one-dimensional Ce:LuPO4 nanorods doped with 0.1 mol % Ce3+ possess the best performance among the as-prepared samples. The significant anisotropy of Ce:LuPO4 nanorods can result in a larger specific surface area and enhanced luminescence properties. Moreover, the improved luminescence property of Ce:LuPO4 nanostructtres can also be optimized by increasing the preferential anisotropic chemical bonding architecture to regulate the 5d level of Ce3+. Our work also shows that the photoluminescence emission intensity of ce:LuPO4 nanorods is increased as the surface area normal to their axial direction increases. From the standpoint of crystallization, the luminescence properties of Ce3+ in nano- and microsize matrixes can be well-optimized by controlling the crystalline behavior of the host lattice under proper synthesis conditions.