Background: Despite Ukraine’s large population, few studies have examined social inequalities in health. This study describes Ukrainian educational inequalities in self-rated health and assesses how far psychosocial, material and behavioural factors account for the education gradient in health. Methods: Data were analyzed from the 2007 wave of the Ukrainian Longitudinal Monitoring Survey. Education was categorized as: lower secondary or less, upper secondary and tertiary. In logistic regressions of 5451 complete cases, stratified by gender, declaring less than average health was regressed on education, before and after adjusting for psychosocial, material and behavioural factors. Results: In analyses adjusted for socio-demographic characteristics, compared with those educated up to lower secondary level, tertiary education was associated with lower risk of less than average health for both men and women. Including material factors (income quintiles, housing assets, labour market status) reduced the association between education and health by 55–64% in men and 35–47% in women. Inclusion of health behaviours (physical activity, smoking, alcohol consumption and body mass index) reduced the associations by 27–30% in men and 19–27% in women; in most cases including psychosocial factors (marital status, living alone, trust in family and friends) did not reduce the size of the associations. Including all potential explanatory factors reduced the associations by 68–84% in men and 43–60% in women. Conclusions: The education gradient in self-rated health in Ukraine was partly accounted for by material and behavioural factors. In addition to health behaviours, policymakers should consider upstream determinants of health inequalities, such as joblessness and poverty.