Developing plasmon-enhanced fluorescence (PEF) technology for identifying important biological molecules has a profound impact on biosensing and bioimaging. However, exploration of PEF for biological application is still at a very early stage. Herein, novel PEF-based core-shell nanostructures as a near-infrared fluorescent turn-on sensor for highly sensitive and selective detection of pyrophosphate (PPi) in aqueous solution are proposed. This nanostructure gold nanorod (AuNR)@SiO2@meso-tetra(4-carboxyphenyl) porphyrin (TCPP) contains a gold nanorod core with an aspect ratio of 2.3, a silica shell, and TCPP molecules covalently immobilized onto the shell surface. The silica shell is employed a rigid spacer for precisely tuning the distance between AuNR and TCPP and an optimum fluorescence enhancement is obtained. Due to the quenching effect of Cu2+, the copper porphyrin (TCPP-Cu2+) results in a weak fluorescence. In the presence of PPi, the strong affinity between Cu2+ and PPi can promote the disassembly of the turn-off state of TCPP-Cu2+ complexes, and therefore the fluorescence can be readily restored. By virtue of the amplified fluorescence signal imparted by PEF, this nanosensor obtains a detection limit of 820 x 10(-9) M of PPi with a good selectivity over several anions, including phosphate. Additionally, the potential applicability of this sensor in cell imaging is successfully demonstrated.