The objective of this paper is to estimate the impact of residential job accessibility on female employment probability in the metropolitan areas of Barcelona and Madrid. Following a “spatial mismatch” framework, we estimate a female employment probability equation where variables controlling for personal characteristics, residential segregation and employment potential on public transport network are included. Data used come from Microcensus 2001 of INE (National Institute of Statistics). The research focuses on the treatment of endogeneity problems and the measurement of accessibility variables. Our results show that low job accessibility in public transport negatively affects employment probability. The intensity of this effect tends to decrease with individual’s educational attainment. A higher degree of residential segregation also reduces job probability in a significant way..