Several new diorganodiselenides containing (imino)aryl groups, [2-(RNCH)C6H4]2Se2 [R = Me2NCH2CH2 (4), O(CH2CH2)2NCH2CH2 (5), PhCH2 (6), 2′,6′-iPr2C6H3 (7)] were obtained by reacting [2-{(O)CH}C6H4]2Se2 (3) with RNH2. Treatment of the diselenides 6 and 7 with stoichiometric amounts of K-selectride or Na resulted in isolation of the selenolates K[SeC6H4(CHNCH2Ph)-2] (9) and Na[SeC6H4(CHNC6H3iPr2-2′,6′)-2] (10), respectively. The reaction of potassium selenolates with anhydrous ZnCl2 (2 : 1 molar ratio) gave Zn[SeC6H4(CHNCH2Ph)-2]2 (11) and Zn[SeC6H4(CHNC6H3iPr2-2′,6′)-2]2 (12). When the dark green solution obtained from diselenide 7 and an excess of Na (after removal of the unreacted metal) was reacted with anhydrous ZnCl2 a carbon–carbon coupling reaction occurred and the 9,10-(2′,6′-iPr2C6H3NH)2C14H10 (8) species was obtained. The compounds were investigated in solution by multinuclear NMR (1H, 13C, 77Se, including 2D and variable temperature experiments) and by mass spectrometry. The molecular structures of 6, 8, 11 and 12 were established by single-crystal X-ray diffraction. All compounds are monomeric in the solid state. In the diselenide 6 the (imino)aryl group acts as a (C,N)-ligand resulting in a distorted T-shaped coordination geometry of type (C,N)SeX (X = Se). For the zinc complexes 11 and 12 the (Se,N) chelate pattern of the selenolato ligands results in tetrahedral Zn(Se,N)2 cores.