Diffusive samplers were used to measure the vertical concentrations of benzene, toluene, n-hexane, cyclohexane, ethylbenzene and o-, m- and p-xylenes on both sides of two NS-oriented street canyons in Murcia (Spain) during a 5-day period. Non-dimensional relationships of concentration and height were calculated in order to study the behaviour of their concentration vertical profiles. The results show that the vertical profiles of benzene, toluene, n-hexane and cyclohexane concentrations were similar in both streets and on both sides of each street. Some differences were found in vertical profiles between streets and sides for ethylbenzene and xylenes, probably due to their higher affinity for adsorption into building materials. The similarities found for the first set of VOCs suggest that the dynamics of the dispersion was the same for both streets and was mainly influenced by microscale thermal effects. Finally, the concentration measurements of benzene, toluene, n-hexane, cyclohexane, and ethylbenzene were adjusted to expressions in the form c = c 0(h/h 0) A , and a regression coefficient R 2 = 0.962 (p = 0.0000) was obtained. The decreasing concentration of these compounds with height should be taken into account when assessing population exposure to these pollutants.