Night-time OH levels have been determined for UK urban surface environments using two methods, the decay and steady state approximation methods. Measurement data from the UK National Environmental Technology Centre archive for four urban sites (Bristol, Harwell, London Eltham and Edinburgh) over the time period of 1996 to 2000 have been used in this study. Three reactive alkenes, namely isoprene, 1,3-butadiene and trans-2-pentene were chosen for the calculation of OH levels by the decay method. Hourly measurements of NO, NO2, O3, CO and 20 VOCs were used to determine night-time OH level using the steady state approximation method. Our results showed that the night-time OH levels were in the range of 1 x×105 -1× 106 molecules/cm3 at these four urban sites in the UK. The application of a /-test of these analyses indicated that except Bristol, there was no significant difference between the OH levels found from the decay and steady state approximation methods. Night-time levels of the OH radical appeared to peak in summer and spring time tracking the night-time O3 levels which also passed through a maximum at this time.