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Abstract: In situ measurements of nitrogen dioxide (NO2) concentrations were conducted at an urban site in Tokyo (35°71′N, 139°76′E), Japan during the summers of 2007–2009. A chemiluminescence instrument equipped with a molybdenum oxide converter (Mo-CL) and a laser-induced fluorescence (LIF) instrument were used simultaneously for determining the ambient NO2 concentrations. A tight linear correlation between the NO2 concentrations determined by the LIF and Mo-CL techniques was evident except for high ozone concentration periods over 50 ppbv. During the high ozone episodes, correlation plots of the NO2 concentrations between Mo-CL and LIF techniques indicated an overestimation of Mo-CL NO2. To examine in detail the systematic differences between two techniques, a thermal dissociation laser-induced fluorescence (TD-LIF) instrument was employed in the summer of 2009 to measure total peroxy nitrates (ΣPNs) and total reactive nitrogen (NO z ). We found that the ΣPNs concentrations correlated well with the discrepancies in NO2 concentrations determined by the Mo-CL and LIF techniques. This result suggests that peroxy nitrate species significantly contribute to the observed interference in the Mo-CL measurements under high O3 concentrations in our observation at the urban site in Tokyo. [Copyright &y& Elsevier]