Sedentary behavior, which is highly prevalent among office workers, is associated with multiple health disorders, including those of the musculoskeletal and cardiometabolic systems. Although prior studies looked at postures or physical activity during work or leisure time, few analyzed both posture and movement throughout the entire day. This cross-sectional pilot study examined the movement behavior of sedentary office workers during both work and leisure time to explore its association with musculoskeletal discomfort (MSD) and cardiometabolic health indicators. Twenty-six participants completed a survey and wore a thigh-based inertial measuring unit (IMU) to quantify the time spent in different postures, the number of transitions between postures, and the step count during work and leisure time. A heart rate monitor and ambulatory blood pressure cuff were worn to quantify cardiometabolic measures. The associations between movement behavior, MSD, and cardiometabolic health indicators were evaluated. The number of transitions differed significantly between those with and without MSD. Correlations were found between MSD, time spent sitting, and posture transitions. Posture transitions had negative correlations with body mass index and heart rate. Although no single behavior was highly correlated with health outcomes, these correlations suggest that a combination of increasing standing time, walking time, and the number of transitions between postures during both work and leisure time was associated with positive musculoskeletal and cardiometabolic health indicators among sedentary office workers and should be considered in future research.