Dacitic rocks, often indicative of crustal recycling on Earth, have been identified in some regions on Mars, as have possible hydrothermally/aqueously-altered dacites. To enable more robust identification of unaltered and altered dacites on Mars and other planetary bodies, we undertook a spectroscopic-structural-compositional study of altered and unaltered dacites from a dacitic volcanic region in Methana, Greece. Dacites erupted in this region range from fresh to pervasively hydrothermally altered, resulting in friable, Si-enriched products, as well as fumarolic deposition of Si and S-rich precipitates. Spectrally, fresh dacites are unremarkable in the 0.35–2.5µm region with low, generally flat, reflectance and few, if any, absorption bands. Dacite infrared spectra exhibit Si-O absorption features in the 8–10µm region (which are characteristic of Si-bearing rocks, in general). With increasing alteration, reflectance over the 0.35–2.5µm range increases, absorption bands in the 1.4 and 1.9µm region, associated with H2O/OH, and in the 2.2–2.3µm region, associated with SiOH, become deeper, Fe3+-associated absorption bands in the 0.43 and 0.9µm region appear, and the Christiansen feature near 8µm moves to shorter wavelengths. Silica-rich coatings appear to be spectrally indistinguishable from Si-rich alteration. Alteration-formed sulfates may be detectable by the presence of diagnostic absorption features in the 0.35–2.5µm region. Spectral similarities between different poorly crystalline high-Si phases make it difficult to uniquely determine the processes that formed high-Si surfaces that have been identified on Mars. However, the samples described here show a variety of spectral features that correspond to variable amounts of alteration. We find a similar range of spectral features, likely due to similar phases, on Mars, perhaps indicating a similar range of alteration environments. Comparison of laboratory spectra to Mars observational data also suggests that the major Si-rich regions likely consist of assemblages that more mineralogically complex than those included in this study.