Among different factors, photosensitizer (PS) is one of the most important factors for prospective application of PDT. Hematoporphyrin (HP) is a kind of endogenous photosensitizer. However, due to obvious photo-induced side toxicity, short excitation wavelength and poor tissue penetration depth, it was restricted to further PDT. Herein, a new near-infrared (NIR) photosensitizer system based on luminescence resonance energy transfer (LRET) is developed. In this system, upconversion nanorods (UCNRs) were surface modified by HP derivatives via direct coordination reaction. Firstly, uniform UCNRs (NaYF4:Yb3+, Tm3+) were successfully synthesized by a high-temperature solvent method. The morphology and crystalline of UCNRs were observed by transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). The luminescence property was studied by fluorescence spectrophotometer (FL). Secondly, hydroxyl groups of hematoporphyrin HP were selectively conjugated with PEG chain to obtain PEGylated HP (HP-diPEG). The che