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This study aimed to assess sitting time and number of steps taken each day, and the relationships between these variables, in a sample of working Australian adults. Workers (N = 185) wore a pedometer for 7 days and recorded the number of steps taken and time spent sitting each day. Average time spent sitting on weekdays was 9.4 (SD = 2.40) hr, with about half spent sitting at work. Despite this, the average steps taken each day (M = 8,873, SD = 2,757) was higher on weekdays than on weekend days. There was a clear inverse relationship between sitting time at work and number of steps taken on weekdays, r = -.34, p < .001); those in the highest tertile for sitting time reported about 3,000 fewer daily steps. Workers in managerial and professional occupations reported more time sitting at work (M = 6.2 hr per day) and lower weekday step counts (M = 7,883, N = 43) than technical (M = 3.3 hr sitting at work and 10,731 weekday steps, N = 33) and blue collar workers (M = 1.6 hours sitting and 11,784 steps, N = 11). The findings suggest those whose daily work involves long hours of sitting should be the focus of efforts to promote physical activity both within and outside the workplace.