Numerous strategies have been proposed to classify brain tissues into gray matter (GM), white matter (WM) and cerebrospinal fluid (CSF). However, many of them fail when classifying specific regions with low contrast between tissues. In this work, we propose an alternative pseudo multispectral classification (PMC) technique using CIE LAB spaces instead of gray scale T1-weighted MPRAGE images, combined with a new preprocessing technique for contrast enhancement and an optimized iterative K-means clustering. To improve the accuracy of the classification process, gray scale images were converted to multispectral CIE LAB data by applying several transformation matrices. Thus, the amount of information associated with each image voxel was increased. The image contrast was then enhanced by applying a real time function that separates brain tissue distributions and improve image contrast in certain brain regions. The data were then classified using an optimized iterative and convergent K-means classifier. The performance of the proposed approach was assessed using simulation and in vivo human studies through comparison with three common software packages used for brain MR image segmentation, namely FSL, SPM8 and K-means clustering. In the presence of high SNR, the results showed that the four algorithms achieve a good classification. Conversely, in the presence of low SNR, PMC was shown to outperform the other methods by accurately recovering all tissue volumes. The quantitative assessment of brain tissue classification for simulated studies showed that the PMC algorithm resulted in a mean Jaccard index (JI) of 0.74 compared to 0.75 for FSL, 0.7 for SPM and 0.8 for K-means. The in vivo human studies showed that the PMC algorithm resulted in a mean JI of 0.92, which reflects a good spatial overlap between segmented and actual volumes, compared to 0.84 for FSL, 0.78 for SPM and 0.66 for K-means. The proposed algorithm presents a high potential for improving the accuracy of automatic brain tissues classification and was found to be accurate even in the presence of high noise level.