This research pioneers the application of a machine learning framework to predict the perceived productivity of office workers using physiological, behavioral, and psychological features. Two approaches were compared: the baseline model, predicting productivity based on physiological and behavioral characteristics, and the extended model, incorporating predictions of psychological states such as stress, eustress, distress, and mood. Various machine learning models were utilized and compared to assess their predictive accuracy for psychological states and productivity, with XGBoost emerging as the top performer. The extended model outperformed the baseline model, achieving an R2 of 0.60 and a lower MAE of 10.52, compared to the baseline model’s R2 of 0.48 and MAE of 16.62. The extended model’s feature importance analysis revealed valuable insights into the key predictors of productivity, shedding light on the role of psychological states in the prediction process. Notably, mood and eustress emerged as significant predictors of productivity. Physiological and behavioral features, including skin temperature, electrodermal activity, facial movements, and wrist acceleration, were also identified. Lastly, a comparative analysis revealed that wearable devices (Empatica E4 and H10 Polar) outperformed workstation addons (Kinect camera and computer-usage monitoring application) in predicting productivity, emphasizing the potential utility of wearable devices as an independent tool for assessment of productivity. Implementing the model within smart workstations allows for adaptable environments that boost productivity and overall well-being among office workers.