In the European context, Spain has a consolidated trajectory in the study of polycentrism; a number of studies have identified, measured and created new methods to identify subcenters. Polycentrism has been widely studied from the morphological and functional perspective, both intra-metropolitan and regional scales. However, little or no attention has been put to the impact of polycentric structures on the efficiency of urbanisation. In this paper, we explore the relationship between polycentricity and labor mobility. Starting from the mobility matrix contained in the Population Census and some previous studies, we have built a series of indicators to measure the incidence of polycentricity on the distances travelled by the working population. In addition, once the structure of the spatial distribution of employment and population has been controlled by the algorithm of M. White 1988, we study, using a statistical model, the relationship between the excess of labor mobility and different urban indicators. The results show that polycentricity effectively reduces mobility, at the time that other obvious urban attributes such as infrastructures (both intended for cars and public transportations) and other planning features, such as the employment to housing ratio and the specialisation in manufacturing, increase it. Conversely, the diversity of housing reduces mobility. These findings show clear implications for urban policies.