Gold nanoclusters (Au NCs) belong to a class of materials that is highly fluorescent and biocompatible. Bovine serum albumin (BSA) protected gold nanoclusters (BSA-Au NCs) have been extensively used in biological applications due to their easy synthesis and relatively high quantum yield. Therefore, understanding the behavior of BSA-Au NCs in different chemical and physical environments is essential to enhance their application in biological systems. In this study, we investigated the effect of plasmonic nanostructures with different localized surface plasmon resonance (LSPR) wavelengths on the behavior of BSA-Au NCs by recording time-dependent fluorescence spectra in the presence of silver nanoparticles (AgNPs) with various shapes. However, we did not observe any conclusive LSPR-wavelength-dependent fluorescent behavior. Additionally, the fluorescence intensity of BSA-Au NCs exhibited gradual decay under light excitation, even at several hundred μW/cm2 in a fluorescence spectrometer, indicating that they are not as photostable as previously assumed. We found further that the photostability of BSA-Au NCs is affected by the wavelength of the incident light (370, 420, 480, and 550 nm), which can be accurately described using bi-exponential decay functions. Our study provides an easy in situ method to evaluate the photostability of Au NCs under different-wavelength light irradiation using a commercial fluorescence spectrometer.