The 90K solid-state structures, room temperature absorption, and room temperature and 17 K emission spectra of seven different salts of [Cu(I)(bfp)(2)](+) (bfp = 2,9-bis(trifluoromethyl)-1,10-phenanthroline) have been determined. To quantify the distortion of the Cu coordination environment, a distortion parameter zeta is defined that is a combined measure of the flattening, rocking, and wagging distortions of the complex cations. In general, the distortion in the (bfp) cations is less than found previously for Cu(I)(dmp)(2) (dmp = 2,9-dimethyl-1,10-phenanthroline) salts, in particular the flattening is reduced because of the bulkier 2,9-substituents. The 17 K lifetimes range up to 1.8 mus in the series of solids examined and, with the marked exception of the BF(4)(-) salt, correlate linearly with the distortion parameter zeta. The emission wavelength red-shifts with decreasing lifetime, which implies that an increased ground-state distortion is associated with a smaller energy gap.