The atomic mass relations among the mass triplet ^{96}Zr, ^{96}Nb, and ^{96}Mo have been determined by means of high-precision mass measurements using the JYFLTRAP mass spectrometer at the IGISOL facility of the University of Jyväskylä. We report Q values for the ^{96}Zr single and double β decays to ^{96}Nb and ^{96}Mo, as well as the Q value for the ^{96}Nb single β decay to ^{96}Mo, which are Q_{β}(^{96}Zr)=163.96(13), Q_{ββ}(^{96}Zr)=3356.097(86), and Q_{β}(^{96}Nb)=3192.05(16) keV. Of special importance is the ^{96}Zr single β-decay Q value, which has never been determined directly. The single β decay, whose main branch is fourfold unique forbidden, is an alternative decay path to the ^{96}Zr ββ decay, and its observation can provide one of the most direct tests of the neutrinoless ββ-decay nuclear-matrix-element calculations, as these can be simultaneously performed for both decay paths with no further assumptions. The theoretical single β-decay rate has been re-evaluated using a shell-model approach, which indicates a ^{96}Zr single β-decay lifetime within reach of an experimental verification. The uniqueness of the decay also makes such an experiment interesting for an investigation into the origin of the quenching of the axial-vector coupling constant g_{A}.