Time structure has been found to be an important coping mechanism for dealing with the negative effects of unemployment on psychological well-being. This study extends the literature by investigating personality (openness to experience, conscientiousness, extraversion, neuroticism, and proactivity) and role demands (marital status, being the only breadwinner, having children, and household demands) as determinants of time structure during unemployment. In addition, five specific dimensions of time structure were examined: sense of purpose, structured routine, present orientation, effective organization, and persistence. In a sample of 231 Flemish unemployed individuals, we found that sense of purpose and present orientation positively predicted psychological well-being. With respect to personality, openness to experience was negatively related to sense of purpose. Conscientiousness related positively to sense of purpose, structured routine, effective organization, and persistence. Neuroticism related negatively to sense of purpose and present orientation. Proactivity positively predicted structured routine, but was a negative predictor of present orientation and persistence. Regarding role demands, being single and having children were positively related to structured routine. These findings highlight the importance of personality for maintaining time structure during unemployment. (Contains 3 tables.)