Heteroleptic copper(I) complexes of the types [Cu(N,N)(P,P)] and [Cu(N,O)(P,P)], where (P,P) = phosphine (PPh3) or diphosphine (dppb, DPEPHOS, XANTPHOS), (N,N) = pyrrole-2-phenylcarbaldimine, 2PyN: [Cu(2PyN)(PPh3)2] (1), [Cu(2PyN) (dppb)] (2), [Cu(2PyN)(DPEPHOS)] (3), and [Cu(2PyN)(XANTPHOS)] (4), (N,N) = indole-2-phenyl-carbaldimine, 2IndN: [Cu(2IndN)(DPEPHOS)] (8), and (N,O) pyrrole-2-carboxaldehyde, 2PyO: [Cu(2PyO)(DPEPHOS)] (5), [Cu(2PyO)(XANTPHOS)] (6), or (N,O) = indole-2-carboxaldehyde, 2IndO: [Cu(2IndO)(DPEPHOS)] (7), were synthesized and characterized by multinudear NMR spectroscopy, electronic absorption spectroscopy, fluorescence spectroscopy, and X-ray crystallography (1-3, 5-8). The complexes with aldimine ligands are thermally stable, and sublimation of 2-4 was possible at T = 230-250 degrees C under vacuum. All complexes exhibit long-lived emission in solution, in the solid state, and in frozen glasses. The excited states have been assigned as mixed intraligand and metal-to-ligand charge transfer (3)(MLCT + pi-pi*) transitions through analysis of the photophysical properties and DFT calculations on representative examples.