The purpose of this study is to examine the relationship of personal and perceived organizational values, and congruence between them with work behavior and its components (task performance, organizational citizenship behavior and adaptive behavior), while controlling for gender, age and tenure. Additionally, this research has examined whether personal or organizational values have a greater predictive strength in predicting work behavior.For that purpose, a convenience sample of 217 subjects from several middle-scale and large-scale organizations completed the following set of instruments: Demographic Questionnaire, Job Performance Scale, Citizenship Performance Scale, Coping Orientation to Problems Experienced, and Personal and Organizational Values Scale. Gathered data was analysed using several hierarchical regression analysis.The results show that personal and organizational values are significant predictors of all aspects of work behavior. Demographic characteristics and congruence in the values of employees and the organization are not significant predictors of work behavior component. Furthermore, the results show that both personal and organizational values have a similar predictive power in the prediction of task performmance, organizational citizenship behavior and problem-oriented adaptive behavior, while personal values proved to be stronger predictors of behavior focused on the emotions and avoidance. This partially confirms the hypothesis on demographic variables, personal and organizational values, and congruence between personal and organizational values as predictors of some aspects of work behavior.