We have shown that crystals of the highly emissive copper(I) compounds [Cu(POP)(dmp)]tfpb, [Cu(xantphos)(dmp)]tfpb, [Cu(xantphos)(dipp)]tfpb, and [Cu(xantphos)(dipp)]pftpb, (where POP = bis[2-(diphenylphosphino)phenyl]ether; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; dmp = 2,9-dimethyl-1,10-phenanthroline; dipp = 2,9-diisopropyl-1,10-phenanthroline (dipp); tfpb- = tetrakis(bis-3,5-trifluoromethylphenylborate); and pftpb = tetrakis(pentfluorophenyl)borate) are oxygen gas sensors. The sensing ability correlates with the amount of void space calculated from the crystal structures. The compounds exhibit linear Stern-Volmer plots with reproducible KSV constants from sample to sample; these results reinforce the observations that the sensing materials are crystalline and the sensing sites are homogeneous within the crystals. The long lifetime (∼30 μs), high emission quantum yield (β = 0.66), appreciable KSV value (5.65), and very rapid response time (51 ms for the 95% return constant) for [Cu(xantphos)(dmp)]tfpb are significantly better than those for the [Cu(NN) 2]tfpb complexes studied previously and compare favorably with [Ru(4,7-Me2phen)3](tfpb)2, (KSV = 4.76; 4,7-Me2phen = 4,7-dimethyl-1,10- phenanthroline). The replacement of precious metals (like Ru or Pt) with copper may be technologically significant and the new compounds can be synthesized in one or two steps from commercially available starting materials. The strictly linear Stern-Volmer behavior observed for these systems and the absence of a polymer matrix that might cause variability in sensor to sensor sensitivity may allow a simple single-reference point calibration procedure, an important consideration for an inexpensive onetime limited use sensor that could be mass produced.