Given an ageing population and increased participation by women in the labour force, the relationship between unpaid care and the availability of women to the labour force is gaining in importance as an issue. This article assesses the impact of unpaid care on transitions into employment by women aged between 45 and 59 years. It uses the German Socio-Economic Panel (SOEP) from the years 2001–2014 to estimate Cox regression models for 6,201 employed women. The results indicate that women with higher caring responsibilities and women with lower caring responsibilities are heterogeneous in terms of the socio-economic characteristics that they exhibit: higher-intensity care providers tend to have a lower level of educational attainment and a weaker attachment to the labour force than women with less-intensive caring responsibilities. Furthermore, while women with more-intensive caring roles are highly likely to exit the labour market altogether, female carers with less-intensive roles seem to be able to combine work and care better. These results highlight the importance of providing more affordable institutional and professional care services, especially for low- and medium-income families.