The electronic and structural properties of ten heteroleptic [Cu(NN)(PP)](+) complexes have been investigated. NN indicates 1,10-phenanthroline (phen) or 4,7-diphenyl-1,10-phenanthroline (Bphen); each of these ligands is combined with five PP bis-phosphine chelators, i.e., bis-(diphenylphosphino)methane (dppm), 1,2-bis-(diphenylphosphino)ethane (dppe), 1,3-bis-(diphenylphosphino)propane (dppp), 1,2-bis-(diphenylphosphino)benzene (dppb), and bis[(2diphenylphosphino)phenyl] ether (POP). All complexes are mononuclear, apart from those based on dppm, which are dinuclear. Experimental data- also taken from the literature and including electrochemical properties, X-ray crystal structures, UV-vis absorption spectra in CH2Cl2, luminescence spectra and lifetimes in solution, in PMMA, and as powders- have been rationalized with the support of density functional theory calculations. Temperature dependent studies (78-358 K) have been performed for selected complexes to assess thermally activated delayed fluorescence. The main findings are (i) dependence of the ground-state geometry on the crystallization conditions, with the same complex often yielding different crystal structures; (ii) simple model compounds with imposed C-2 nu symmetry [Cu(phen)(PX3)(2)](+); X = H or CH3) are capable of modeling structural parameters as a function of the P-Cu-P bite angle, which plays a key role in dictating the overall structure of [Cu(NN)(PP)](+) complexes; (iii) as the P-Cu-P angle increases, the energy of the metal-to-ligand charge transfer absorption bands linearly increases; (iv) the former correlation does not hold for emission spectra, which are red-shifted for the weaker luminophores; (v) the larger the number of intramolecular pi-interactions within the complex in the ground state, the higher the luminescence quantum yield, underpinning a geometry locking effect that limits the structural flattening of the excited state. This work provides a general framework to rationalize the structure property relationships of [Cu(NN)(PP)](+), a class of compounds of increasing relevance for electroluminescent devices, photoredox catalysis, and solar-to-fuels conversion, which so far have been investigated in an unsystematic fashion, eluding a comprehensive understanding.