Background Active living approaches seek to promote physical activity and reduce sedentary time across different domains, including through active travel. However, there is little information on how movement behaviours in different domains relate to each other. We used compositional data analysis to explore associations between active commuting and patterns of movement behaviour during discretionary time. Methods and findings We analysed cross-sectional and longitudinal data from the UK Biobank study. At baseline (2006–2010) and follow up (2009–2013) participants reported their mode of travel to work, dichotomised as active (walking, cycling or public transport) or inactive (car). Participants also reported activities performed during discretionary time, categorised as (i) screen time; (ii) walking for pleasure; and (iii) sport and do-it-yourself (DIY) activities, summed to produce a total. We applied compositional data analysis to test for associations between active commuting and the composition and total amount of discretionary time, using linear regression models adjusted for covariates. Adverse events were not investigated in this observational analysis. The survey response rate was 5.5%. In the cross-sectional analysis (n = 182,406; mean age = 52 years; 51% female), active commuters engaged in relatively less screen time than those who used inactive modes (coefficient -0.12, 95% confidence interval [CI] -0.13 to -0.11), equating to approximately 60 minutes less screen time per week. Similarly, in the longitudinal analysis (n = 4,323; mean age = 51 years; 49% female) there were relative reductions in screen time in those who used active modes at both time points compared with those who used inactive modes at both time points (coefficient -0.15, 95% confidence interval [CI] -0.24 to -0.06), equating to a difference between these commute groups of approximately 30 minutes per week at follow up. However, as exposures and outcomes were measured concurrently, reverse causation is possible. Conclusions Active commuting was associated with a more favourable pattern of movement behaviour during discretionary time. Active commuters accumulated 30–60 minutes less screen time per week than those using inactive modes. Though modest, this could have a cumulative effect on health over time.