We present an integral study on the photonic response of AuGe nanoparticles (NPs) to establish a correlation between different parameters such as NP size, volume, and distribution over different substrates (n + GaAs, semiconducting GaAs) having different film thicknesses (∼5, ∼10 nm) at different annealing temperatures (573 and 673 K) subjected to repeated and stepped annealing cycles. The structural characterization of overlayer growth and formation of AuGe nanoclusters/ NPs is correlated with unusual plasmonic response measured during photonic characterization. The morphological changes induced by stepped annealing of the AuGe/GaAs system resulted in enhanced light emission and favorable tuning of plasmon frequency. A larger photoluminescence enhancement is measured with the fifth anneal, which is found to be related to the enhanced NP reflectance and is in good theoretical agreement with the Drude−Lorentz model. The numerical negative real permittivity "ε 1 " confirms the plasmonic impact, while X-ray photoelectron spectroscopy studies reveal the unique intermixing phenomena of AuGe and GaAs at the interface due to annealing. Additionally, ultrafast studies depict the periodic absorbance in the below-band-gap region of GaAs resembling an EL2-state-like behavior. The AuGe NPs embedded/adhered on a light-emitting surface thus offer both the ease and flexibility for tuning the plasmon resonance frequency, to attain tweaked and enhanced light-matter coupling, which can be concluded as plasmon-induced interfacial charge-transfer transition phenomena. The enhanced light coupling enhances both the photovoltaic conversion efficiency and quantum efficiency, thereby enabling increased solar cell fill factor and responsivity enhancement in photovoltaic devices such as photodetectors and thermal imagers.