To evaluate the release mechanism of volatile organic species (VOCs) from solar illuminated snowpacks, this study used proton transfer reaction–mass spectrometry (PTR-MS) for the first time to study VOCs within Arctic snow and to compare these results to VOC release from illuminated snow in the laboratory. The field measurements were conducted in April during the 2009 Ocean–Atmosphere–Sea Ice–Snowpack (OASIS) campaign in Barrow, Alaska, whereas in the laboratory four natural snow samples, from the Arctic (Alert, Nunavut), a rural site (Egbert, Ontario), and an urban area (Toronto, Ontario), were exposed to a Xe arc lamp with a 295 nm longpass filter. Similar VOCs were observed in both the field and laboratory experiments suggesting that these light-driven processes occur not only in polar regions but in midlatitude snows as well. Also, because the laboratory samples were temperature controlled, we conclude that the release mechanism is primarily photochemical and not temperature mediated. The snow composition may have influenced VOC production because aged Toronto snow samples, with both the highest total organic carbon content and concentration of oxidant precursors (i.e., NO3−), exhibited the largest production of VOCs upon irradiation.