An efficient method for oxidative trifluoromethylselenolation/N-acylation of indoles with excess [Me4N][SeCF3] in the presence of acyl peroxides and their derivatives is described. The reaction is easy to handle, proceeds smoothly at room temperature under metal-free conditions, and shows advantages such as good functional group tolerance, excellent regioselectivity, and compatibility of a number of substrates, producing 1-acyl and 3-trifluoromethylselanyl substituted indoles in good yields. Acyl peroxides and peroxycarboxylic acid behave as both oxidants and acyl sources in the transformation. This one-pot procedure provides a convenient access to a new class of indole derivatives, representing the first trifluoromethylselanyl bifunctionalization of indoles with the nucleophilic [Me4N][SeCF3] reagent.