Biogenic VOC emissions are often dominated by 2-methyl-1,3-butadiene (isoprene) and 2-methyl-3-buten-2-ol (232 MBO). Here we explore the possibility to selectively distinguish these species using NO+ as a primary ion in a conventional PTR-MS equipped with an SRI unit. High purity of NO+ (>90 %) as a primary ion was utilized in laboratory and field experiments using a conventional PTR-TOF-MS. Isoprene is ionized via charge transfer leading to the major product ion C5H+8 (>99 %) (e.g. Spanel and Smith, 1998). 232 MBO undergoes a hydroxide ion transfer reaction resulting in the major product ion channel C5H+9 (>95 %) (e.g. Amelynck et al., 2005). We show that both compounds are ionized with little fragmentation (<5 %) under standard operating conditions. Typical sensitivities of 11.1±0.1 (isoprene) and 12.9±0.1 (232 MBO) ncps ppbv−1 were achieved, which correspond to limit of detections of 18 and 15 pptv respectively for a 10 s integration time. Sensitivities decreased at higher collisional energies. Calibration experiments showed little humidity dependence. We tested the setup at a field site in Colorado dominated by ponderosa pine, a 232MBO emitting plant species. Our measurements confirm 232MBO as the dominant biogenic VOC at this site, exhibiting typical average daytime concentrations between 0.2–1.4 ppbv. The method is able to detect the presence of trace levels of isoprene at this field site (90–250 ppt) without any interference from 232 MBO, which would not be feasible using H3O+ ionization chemistry, and which currently also remains a challenge for other analytical techniques (e.g. gas chromatographic methods)