The present study examines whether negative and positive affectivity (NA and PA, respectively) predict different forms of work-to-family conflict (WFC-time, WFC-strain, WFC-behavior) and enrichment (WFE-development, WFE-affect, WFE-capital) beyond job characteristics (workload, autonomy, variety, workplace support). Furthermore, interactions between job characteristics and trait affectivity while predicting WFC and WFE were examined. Using a large sample of Slovenian employees (N = 738), NA and PA were found to explain variance in WFC as well as in WFE above and beyond job characteristics. More precisely, NA significantly predicted WFC, whereas PA significantly predicted WFE. In addition, several interactive effects were found to predict forms of WFC and WFE. These results highlight the importance of trait affectivity in work-family research. They provide further support for the crucial impact of job characteristics as well.