Detailed comparative theoretical and experimental study of electronic properties and spin structure was carried out for a series of Pb-based quaternary compounds PbBi 2 Te 4−x Se x. For all values of x, these compounds are theoretically predicted to be topological insulators, possessing at high Se content a remarkably large band gap and a Dirac point isolated from bulk states. Using spin-and angle-resolved photoemission spectroscopy, it was shown that the PbBi 2 Te 2 Se 2 and PbBi 2 Te 1.4 Se 2.6 compounds are characterized by well-defined spin-polarized topological surface state in the bulk gap. To define the probable distribution of atoms over the atomic sites for these samples, we performed ab initio calculations in ordered and disordered configurations of the unit cell. We found that theoretical calculations better reproduce photoemission data when Te atoms are placed in the outermost layers of the septuple layer block.