The purpose of this study was to use ecological momentary assessment to investigate the patterning of physical activity and sedentary behaviours in UK adolescents and to examine if different lifestyle groups differ on key explanatory variables. A total of 1,371 (38% boys, mean age 14.7 years) adolescents completed diaries every 15 min for 3 weekdays outside of school hours and 1 weekend day. Cluster analysis yielded five-cluster solutions for both boys and girls to explain the grouping of sedentary behaviours and physical activity. The clusters demonstrated that adolescents engage in many leisure time behaviours but have one activity that predominates. Active adolescents spend more time outside and more time with their friends. Few demographic and environmental variables distinguished between clusters. The findings suggest a potential need for different behavioural targets in interventions to reduce sedentary behaviour in sub groups of the adolescent population. Further research is required to examine the modifiable determinants of different sedentary lifestyles among young people.