The use of copper selenide nanocatalyst for an efficient and regioselective cross-dehydrogenative coupling (CDC) of tertiary amines with terminal alkynes in the presence of tert-butyl hydroperoxide as the oxidant is demonstrated for the first time. The catalyst comprising of unique Cu6Se4.5 nanopartides synthesized from a single source precursor CuSePh, is required in much lower amount (1 mol%), and is recyclable up to four reaction cycles with slight loss in activity. The reaction can be executed in the absence of solvent, is applicable to aromatic, benzylic, and aliphatic tertiary amines, and furnishes propargylamines in moderate to good yields. (C) 2016 Elsevier B.V. All rights reserved.