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In this study, we explored the potential of applying biosensors based on silicon nanowire field-effect transistors (bio–NWFETs) as molecular absorption sensors. Using quercetin and Copper (Cu2+) ion as an example, we demonstrated the use of an opto–FET approach for the detection of molecular interactions. We found that photons with wavelengths of 450 nm were absorbed by the molecular complex, with the absorbance level depending on the Cu2+ concentration. Quantitative detection of the molecular absorption of metal complexes was performed for Cu2+ concentrations ranging between 0.1 μM and 100 μM, in which the photon response increased linearly with the copper concentration under optimized bias parameters. Our opto–FET approach showed an improved absorbance compared with that of a commercial ultraviolet-visible spectrophotometry.