Objectives: We identified profiles of wake-time movement behaviours (sedentary behaviours, light intensity physical activity and moderate-to-vigorous physical activity) based on accelerometer-derived features among older adults and then examined their association with all-cause mortality. Methods: Data were drawn from a prospective cohort of 3991 Whitehall II accelerometer substudy participants aged 60–83 years in 2012–2013. Daily movement behaviour profiles were identified using k-means cluster analysis based on 13 accelerometer-assessed features characterising total duration, frequency, bout duration, timing and activity intensity distribution of movement behaviour. Cox regression models were used to assess the association between derived profiles and mortality risk. Results: Over a mean follow-up of 8.1 (SD 1.3) years, a total of 410 deaths were recorded. Five distinct profiles were identified and labelled as 'active' (healthiest), 'active sitters', 'light movers', 'prolonged sitters', and 'most sedentary' (most deleterious). In model adjusted for sociodemographic, lifestyle, and health-related factors, compared with the 'active' profile, 'active sitters' (HR 1.57, 95%¿CI 1.01 to 2.44), 'light movers' (HR 1.75, 95%¿CI 1.17 to 2.63), 'prolonged sitters' (HR 1.67, 95%¿CI 1.11 to 2.51), 'most sedentary' (HR 3.25, 95%¿CI 2.10 to 5.02) profiles were all associated with a higher risk of mortality. Conclusion: Given the threefold higher mortality risk among those with a 'most sedentary' profile, public health interventions may target this group wherein any improvement in physical activity and sedentary behaviour might be beneficial.