In functional neuroimaging, a crucial problem is to localize active sources within the brain non-invasively, from knowledge of electromagnetic measurements outside the head. Identification of point sources from boundary measurements is an ill-posed inverse problem. In the case of electroencephalography (EEG), measurements are only available at electrode positions, the number of sources is not known in advance and the medium within the head is inhomogeneous. This paper presents a new method for EEG source localization, based on rational approximation techniques in the complex plane. The method is used in the context of a nested sphere head model, in combination with a cortical mapping procedure. Results on simulated data prove the applicability of the method in the context of realistic measurement configurations.