The results of a solid-state Cu-63/65 and P-31 NMR investigation of several copper(I) complexes with functionalized 3-(2'-pyridy1)-1,2,4-triazole and phosphine ligands that have shown potential in the preparation of photoluminescent devices are reported. For each complex studied, distinct NMR parameters, with moderate Cu-63 nuclear quadrupolar coupling constant (C-Q) values ranging from -17.2 to -23.7 MHz, are attributed to subtle variations in the distorted four-coordinate environments about the copper nuclei. The spans of the copper chemical shift (CS) tensors, delta(11)-delta(33), for the mono- and bisphosphine complexes are also similar, ranging from 1000 to 1150 ppm, but that for a complex with a strained bidentate phosphine ligand is only 650 ppm. The effects of residual dipolar and indirect spin spin coupling arising from the Cu-63/65- P-31 spin pairs, observed in the solid-state P-31 NMR spectra of these complexes, yield information about the orientations of the copper electric field gradient (EFG) tensors relative to the Cu-P bond. Variable-temperature P-31 NMR measurements for [Cu(bptzH)(dppe)]ClO4 (bptzH = 5-tert-butyl-3-(2'-pyridy1)-1,2,4-triazole; dppe = 1,2-bis(diphenylphosphino)ethane), undertaken to investigate the cause of the broad unresolved spectra observed at room temperature, demonstrate from partial self-decoupling of the Cu-63/65 nuclei, a consequence of rapid quadrupolar relaxation. Ab initio calculations of copper EFG and CS tensors were performed to probe relationships between NMR parameters and molecular structure. The analysis demonstrated that C-Q(Cu-63/65) is negative for all complexes studied here and that the largest components of the EFG tensors are generally coincident with delta(11).