Among different green oxidative protocols, I₂ catalyzed DMSO systems have recently received considerable attention being greener, efficient, atom-economical, low-cost, and offering the possibility to perform reactions under safe and mild conditions. Particularly interesting is the application in the chalcogen-chalcogen bond activation that allows the in-situ formation of electrophilic species promoting a number of Se-C bond formation. In these reactions’ iodine acts a catalytic oxidant continuously regenerated by the DMSO that can be used in stoichiometric amount under solvent free conditions. Methoxyselenylation reactions can be performed at room temperature but the reaction takes over 24 hours to reach appreciable conversion yields. In this paper the activation by the use of a SynLED Parallel Photoreactor® is investigated as an alternative energy source and the results are critically compared with with those previously reported in literature.