Reported on is a photofragmentation two-photon laser-induced fluoresence (PF/TP-LIF) sensor with a demonstrated capability for making simultaneous measurements of NO/NOx/NO2. This instrumental technique is based on the direct spectroscopic detection of NO via the TP-LIF methodology. The measurements of NOx(NO+NO2), and subsequently NO2, is accomplished by the photofragmentation of NO2 at 353 nm via a XeF excimer laser. The resultant NO photofragment is then quantitatively detected using the TP-LIF technique. The laser photolysis efficiency for NO2 is typically 60% for NO2 photolysis cell residence times of less than 0.5 s. The limit of detection (S/N=2) for the described PF/TP-LIF instrument is 3.5 pptv for NO (2 min integration time) and 10 pptv for NO2 (6 min integration time). An assessment of chemical interferences in this system revealed no significant problems. The extension of the PF/TP-LIF methodology to the simultaneous detection of multiple NxOy species is discussed.