Resumen: Background To investigate the associations between combined categories of moderate-to-vigorous physical activity (MVPA) and sedentary behaviour (SB) with markers of adiposity and cardiovascular risk in adults. Methods Overall, 5040 participants (mean age 46.4 years and 59.3% women) from the cross-sectional Chilean National Health Survey 2009-2010 were included in this study. MVPA and SB were measured using the Global Physical Activity questionnaire. Four categories were computed using MVPA- and SB-specific cut-offs ('High-SB & Active', 'Low-SB & Active', 'High-SB & Inactive' and 'Low-SB & Inactive'). Results Compared to the reference group ('High-SB & Inactive'), those in 'High-SB & Active' and 'Low-SB & Active' were less likely to have an obese BMI (OR: 0.67 [0.54; 0.85], P = 0.0001 and 0.74 [0.59; 0.92] P = 0.0007, respectively) and less likely to have metabolic syndrome (OR: 0.63 [0.49; 0.82], P < 0.0001 and 0.72 [0.57; 0.91], P = 0.007), central obesity (OR: 0.79 [0.65; 0.96], P = 0.016 and 0.71 [0.59; 0.84], P < 0.0001), diabetes (OR: 0.45 [0.35; 0.59], P < 0.0001 and 0.44 [0.34; 0.56], P < 0.0001) and hypertension (OR: 0.52 [0.43; 0.63], P < 0.0001 and 0.60 [0.50; 0.72], P < 0.0001), respectively. Conclusions Being physically active and spending less time in SBs was associated with lower adiposity and improvements in cardiovascular risk factors.