Brain tissue segmentation in Magnetic Resonance Imaging is useful for a wide range of applications. Classical approaches exploit the gray levels image and implement criteria for differentiating regions. Within this paper a novel approach for brain tissue joint segmentation and classification is presented. Starting from the estimation of proton density and relaxation times, we propose a novel method for identifying the optimal decision regions. The approach exploits the statistical distribution of the involved signals in the complex domain. The technique, compared to classical threshold based ones, is able to globally improve the classification rate. The effectiveness of the approach is evaluated on both simulated and real datasets.