A facile and efficient method was established for the more productive synthesis of highly fluorescent CePO4:Tb (core) and CePO4:Tb@LaPO4 (core/shell) nanorods (NRs) at low temperature. Subsequently, the surface of the core/shell NRs was functionalized by silica layer (CePO4:Tb@LaPO4@SiO2, core/shell/Si) to enhance the solubility and colloidal stability character in an aqueous and non-aqueous solvent. XRD pattern shows the phase purity, crystallinity and single-crystalline nature of the hexagonal-rhabdophane type structure of NRs, which was further verified from FETEM images. TEM image shows a thin silica layer around the seed core/shell NRs. After coating of silica shell the resulting core/shell NRs have a mean diameter of about 20nm and length up to 100nm. The core/shell NRs demonstrate highest excitation and emission intensity, which was suppressed after silica layer coating due to enhancement in the multiphoton-relaxation process. However, core/shell/Si NRs represent high solubility in an aqueous environment on that basis it could find potential applications in photonic and photonic based biomedical sciences.