AbstractSimultaneous measurements of volatile organic compounds (VOCs) using two PTR‐TOF‐MS instruments were conducted at urban and suburban sites of New Delhi during the winter of 2018. The time series of VOC mixing ratios show substantial variations mainly influenced by local emissions and meteorological conditions. Mixing ratios of methanol (∼28 ppbv), acetaldehyde (7.7 ppbv), acetone (10.6 ppbv), isoprene (2.8 ppbv) and monoterpenes (0.84 ppbv) at the suburban site were higher than those at the urban site, while levels of aromatic VOCs were almost similar. The strong nighttime correlations of isoprene and monoterpenes with CO and benzene at the urban site indicate their predominant anthropogenic origin. Higher emission ratios of ∆VOCs/∆CO and ∆VOCs/∆benzene than those reported for vehicular exhaust suggest the contributions of other sources. In addition to vehicular emissions, episodes of biomass burning, industrial plumes and aged air strongly influenced the levels of VOCs at the suburban site. Despite the predominant primary anthropogenic emissions, the higher daytime enhancements of OVOCs/CO ratios indicate additional contributions of OVOCs from secondary/biogenic sources. The secondary formation of OVOCs in moderately aged air masses was noticeable at the suburban site. Using the source‐tracer‐ratio method, the estimated biogenic contributions of isoprene (71%) and acetone (65%) during daytime at the suburban site were significantly higher than those for the urban site. The photochemical box model simulations suggest that daytime ozone formation was under the VOC‐limited regime. The present study highlights the impact of different emission sources, photochemical processes and meteorological conditions on the composition and concentration of VOCs in the Delhi region.