Mixing ratios of 15 carbonyls and BTEX (benzene, toluene, ethyl benzene, xylenes) were measured for the first time in ambient air of Kolkata, India at three sites from March to June 2006 and their photochemical reactivity was evaluated. Day and nighttime samples were collected on weekly basis. Formaldehyde was the most abundant carbonyl (mean concentration ranging between 14.07 microg m(-3) to 26.12 microg m(-3) over the three sites) followed by acetaldehyde (7.60-18.67 microg m(-3)) and acetone (4.43-10.34 microg m(-3)). Among the high molecular weight aldehydes, nonanal showed the highest concentration. Among the mono-aromatic VOCs, mean concentration of toluene (27.65-103.31 microg m(-3)) was maximum, closely followed by benzene (24.97-79.18 microg m(-3)). Mean formaldehyde to acetaldehyde (1.4) and acetaldehyde to propanal ratios (5.0) were typical of urban air. Based on their photochemical reactivity towards OH. radical, the concentrations of the VOCs were scaled to formaldehyde equivalent, which showed that the high molecular weight carbonyls and xylenes contribute significantly to the total OH-reactive mass of the VOCs. Due to the toxic effect of the VOCs studied, an assessment for both cancer risk and non-cancer hazard due to exposure to the population were calculated. Integrated life time cancer risk (ILTCR) due to four carcinogens (benzene, ethyl benzene, formaldehyde and acetaldehyde) and non-cancer hazard index for the VOCs at their prevailing level were estimated to be 1.42E-04 and 5.6 respectively.