Background Life expectancy increased in industrialized countries, but inequalities in health and mortality by socioeconomic position (SEP) still persist. Several studies have documented educational inequalities, yet the association between health and employment status remains unclear. However, this is an important issue considering the instability of the labour market and the fact that unemployment now also touches 'non-traditional groups' (e.g. the high-educated). This study will 1) probe into the association between unemployment and cause-specific mortality; 2) look into the possible protective effect of sociodemographic variables; 3) assess the association between unemployment, SEP, gender and cause-specific mortality. Material and methods Individually linked data of the Belgian census (2001) and Register data on emigration and cause-specific mortality during 2001-2011 are used. The study population contains the Belgian population eligible for employment at census, based on age (25-59 years) and being in good health. Both absolute and relative measures of all-cause and cause-specific mortality by employment status have been calculated, stratified by gender and adjusted for sociodemographic and socioeconomic indicators. Results Unemployed men and women were at a higher risk for all-cause and cause-specific mortality compared with their employed counterparts. The excess mortality among unemployed Belgians was particularly high for endocrine and digestive diseases, mental disorders, and falls, and more pronounced among men than among women. Other indicators of SEP did only slightly decrease the mortality disadvantage of being unemployed. Discussion The findings stress the need for actions to ameliorate the health status of unemployed people, especially for the most vulnerable groups in society.