Two crystal structures of the mononuclear copper(I)-nitrosyl complexes [Cu(L3)(NO)] (1) and [Cu(L3')(NO)1(CIO4) (2) with the related coligands L3(-) (hydrotris(3-tert-butyl-5-isopropyl-1-pyrazolyl)borate) and L3' (tris(3-tert-butyl-5-isopropyl-1-pyrazolyl) methane) are presented. These compounds are then investigated in detail using a variety of spectroscopic methods. Vibrational spectra show nu(N-O) at 1698 cm(-1) and nu(Cu-NO) split at 365/338 cm(-1) for 1, which translates to force constants of 12.53 (N-O) and 1.31 mdyn/angstrom (Cu-NO), respectively. The weak Cu-NO force constant is in agreement with the observed instability of the Cu-NO bond. Interestingly, complex 2 with the neutral coligand LT shows a stronger N-O bond, evident from v(N-O) at 1742 cm-1. This difference is attributed to a true second coordination sphere effect, where the covalency of the Cu(I)-NO bond is not altered. The EPR spectrum of 1 is in agreement with the Cu(l)-NO(radical) electronic structure of the complexes, as obtained from density functional theory (DFT) calculations. In addition, an interesting trend between g(II)(g(z)) and the Cu-N-O angle is established. Finally, high-quality MCD spectra of 1 are presented and assigned using TD-DFT calculations. Based on the in-depth spectroscopic characterization of end-on bound NO to copper(l) presented in this work, it is possible to determine the binding mode of the Cu-NO intermediate of Cu nitrite reductase studied by Scholes and co-workers (Usov, O. M.; Sun, Y.; Grigoryants, V. M.; Shapleigh, J. P.; Scholes, C. P., J. Am. Chem. Soc. 2006, 128, 13102-13111) in solution as strongly bent (similar to 135 degrees) but likely not side-on.