Background: Prolonged sitting is an emerging health risk. However, multi-country comparative sitting data are sparse. This paper reports the prevalence and correlates of sitting time in 32 European countries. Methods: Data from the Eurobarometer 64.3 study were used, which included nationally representative samples (n = 304-1,102) from 32 European countries. Face-to-face interviews were conducted during November and December 2005. Usual weekday sitting time was assessed using the International Physical Activity Questionnaire (short-version). Sitting time was compared by country, age, gender, years of education, general health status, usual activity and physical activity. Multivariable-adjusted analyses assessed the odds of belonging to the highest sitting quartile. Results: Data were available for 27,637 adults aged 15–98 years. Overall, mean reported weekday sitting time was 309 min/day (SD 184 min/day). There was a broad geographical pattern and some of the lowest amounts of daily sitting were reported in southern (Malta and Portugal means 194–236 min/day) and eastern (Romania and Hungary means 191–276 min/day) European countries; and some of the highest amounts of daily sitting were reported in northern European countries (Germany, Benelux and Scandinavian countries; means 407–335 min/day). Multivariable-adjusted analyses showed adults with low physical activity levels (OR = 5.10, CI95 = 4.60-5.66), those with high sitting in their main daily activity (OR = 2.99, CI95 = 2.74-3.25), those with a bad/very bad general health state (OR = 1.87, CI95 = 1.63-2.15) and higher education levels (OR = 1.48, CI95 = 1.38-1.59) were more likely to be in the highest quartile of daily sitting time. Adults within Greece (OR = 2.91, CI95 = 2.51-3.36) and Netherlands (OR = 2.56, CI95 = 2.22-2.94) were most likely to be in the highest quartile. High-sit/low-active participants comprised 10.1% of the sample. Adults self-reporting bad/very bad general health state (OR = 4.74, CI95 = 3.97-5.65), those within high sitting in their main daily activities (OR = 2.87, CI95 = 2.52-3.26) and adults aged ≥65 years (OR = 1.53, CI95 = 1.19-1.96) and were more likely to be in the high-sit/low-active group. Conclusions: Weekday sitting time and its demographic correlates varied considerably across European countries, with adults in north-western European countries sitting the most. Sitting is prevalent across Europe and merits attention by preventive interventions.