An experimental-computational method is used to investigate the spectroscopic behavior of naphthalene on the surface of ice grains. UV-vis diffuse reflectance and fluorescence spectroscopies of naphthalene combined with DFT and ADC(2) calculations provide evidence for the occurrence of excited-state associates. The measured and calculated bathochromic shifts of the S0 → S1 electronic transitions related to naphthalene dimers or naphthalene-ice interactions do not exceed 3 nm. The bands observed in the emission spectrum of frozen naphthalene solutions are assigned to excited dimers of different mutual orientations, naphthalene phosphorescence, and fluorescence of anthracene present as a trace impurity and populated by the energy transfer from excited naphthalene. Photochemical reactivity in/on ice and snow is dependent on the absorption properties and speciation of the compounds present in these media. Hence, within this study, we exploit frozen solutions of naphthalene to demonstrate both the absence of considerable bathochromic shift and a strong tendency to aggregate.