Under near-infrared (NIR) light of 810 nm wavelength for irradiation, a very simple and highly sensitive photoelectrochemical (PEC) biosensing platform has been established using the localized surface plasmon resonance effect of Au nanoparticles (NPs) as signal amplification for the nondestructive analysis of living cells. The water-dispersible Ag2S quantum dots (QDs) synthesized by a one pot method were employed as photoelectrochemically active species, and they exhibited excellent PEC properties irradiated with NIR light which was chosen due to the obvious absorption and fluorescent emission in the NIR light region. After the incorporation of Au NPs on the Ag2S QDs modified ITO electrode, the photoelectric conversion efficiency was greatly increased, at ∼2.5 times that of the pure Ag2S QDs modified electrode. Additionally, 4-mercaptophenylboronic acid (MPBA) molecules, as recognition elements, self-assembled on the electrode surface through Au-S bonds. On the basis of the chemical reaction between sialic acid on the cytomembranes and boric acid of MPBA, the very simple PEC biosensing platform was used for the quantitative determination of MCF-7 cells and dynamic evaluation of cell surface glycan expression under the external stimulus of sialidase. Under NIR light of 810 nm and a potential of 0.15 V, this proposed strategy exhibited a wide linear range from 1 × 102 to 1 × 107 cells/mL, with an experimental detection limit of 100 cells/mL. Importantly, this work provided a promising application for NIR Ag2S QDs coupled with Au NPs in the development of a novel PEC biosensing platform for the nondestructive analysis of biological samples.