The formation of gold–silver alloy nanoparticles (Au–Ag alloy NPs) by a two-step process with a pulsed Nd:YAG laser without any additives is presented. Mixtures of Au and Ag colloidal suspensions were separately obtained by 1064-nm laser ablation of metallic targets immersed in ethanol. Subsequently, the as-mixed colloidal suspensions were reirradiated by laser-induced heating at the second-harmonic generation (532 nm) for different irradiation periods of time. The absorption spectra and morphology of the colloidal alloys were studied as a function of exposure time to laser irradiation. Transmission electron microscopy revealed the formation of monodispersed spherical nanoparticles with a homogeneous size distribution in all the synthesized samples. UV–vis and photoluminescence spectroscopy measurements were also employed to characterize the changes in the light absorption and emission of N719 dye solution with different concentrations of Au–Ag colloidal alloys, respectively. The localized surface plasmon resonance (LSPR) of Au–Ag alloy NPs enhanced the absorption and fluorescence peak of the dye solution. The mixture of dye molecules with a higher concentration of alloy NPs exhibited an additional coupling of dipole moments with the LSPR, thereby contributing to the improvement of the optical properties of the mixture.