Using heart rate (HR) measurements to detect mental stress in naturalistic settings is hampered by the physiological impact of hemodynamic and metabolic demands. Correcting HR for these demands can help isolate fluctuations in HR associated with psychosocial stress responses, a concept termed additional heart rate (aHR). This study examined whether adding predictors for posture, activity type, and lagged movement intensity for the prolonged impact of physical activity (PA) improved aHR estimation across various manipulations of mental stress, posture, and PA in a controlled laboratory environment (n = 197). Accelerometer signals were used to obtain the movement intensity and to classify posture and activity type. Posture, activity type, and lagged movement intensity each led to a significant improvement in HR estimation, as measured by adjusted R2 and root mean squared error. However, HR was overestimated during quiet sitting. The aHR, computed as the difference between observed and predicted HR, generally underestimated observed task‐baseline reactivity but was sensitive to individual differences in reactivity to mental stressors. Between‐subject correlations of aHR with task‐baseline reactivity ranged from 0.62 to 0.93 across conditions. On a within‐subject level, the ability of aHR to differentiate between exposure to physical stress and mental stress was limited (recall = 0.32, precision = 0.31), but better than that of observed HR (recall = 0.02, precision = 0.02). Future research should explore the potential of this novel aHR estimation method in differentiating physical and mental demands on HR in daily life, and its predictive value for health outcomes.