Research in organizational psychology has increasingly focused on understanding the determinants of “green” employee behavior. The present study used a daily diary design to investigate relationships between employees' daily affect, pro-environmental attitude, as well as daily task-related pro-environmental behavior (i.e., the extent to which employees complete required work tasks in environmentally friendly ways), and daily proactive pro-environmental behavior (i.e., the extent to which employees show personal initiative when acting in environmentally friendly ways at work). Fifty-six employees working in small businesses completed a baseline survey and two daily surveys over ten workdays. Daily unactivated positive affect and pro-environmental attitude positively predicted daily task-related pro-environmental behavior. In addition, daily activated positive affect positively predicted daily proactive pro-environmental behavior among employees with a less positive pro-environmental attitude but not among employees with a more positive pro-environmental attitude. These findings suggest that fostering pro-environmental attitudes and, to some extent, positive affect among employees could help organizations to promote pro-environmental behavior in the workplace. Copyright © 2012 John Wiley & Sons, Ltd.