One of the key factors for promoting well-being lies in balancing one’s daily life occupations and the nature of these occupations. Occupation refers to a group of everyday life goal-directed activities which may be associated to any life domain, not necessarily work, such as leisure, education, or self-care. Yet it is not clear what constitutes occupational imbalance, and its association to other factors has not been examined systematically. This study proposed and tested a theoretical model for specifying the structural relationships between occupational imbalance, occupational characteristics, personality and well-being. 288 working adults completed the following questionnaires: Inter-goal Relations Questionnaire (occupational imbalance), Personal Projects Analysis (occupational characteristics), the Big Five Inventory (personality traits) and the Satisfaction with Life Scale (well-being). Twenty-five models were tested using structural equation modeling. All the models fit the data well. Occupational characteristics, with the exception of stress, served as significant mediators between personality and well-being, yet occupational imbalance did not play a significant role across all models. Our findings provide substantial support for the importance of occupation to well-being, however occupational imbalance is still an elusive concept that requires further investigation theoretically and empirically.