We have investigated the possibility of altering the electronic configuration of the niobium oxochloride cluster compound Ti2Nb6Cl14O4 (I) by doping this material with monovalent cations that can fit: into cavities present in its cluster framework. The doping of I with In+ and Tl+ ions resulted in:the formation of MxTi2Nb6Cl14-xO4+x (M = In, x = 0.10, 0.20, 0.27; M = Tl, x = 0.10, 0.20) in which the M+ ions partially occupy these cavities. The crystal structure analysis indicated that the additional charge provided by M+ ions is compensated by substitution of chlorine by oxygen, which leads to the cluster electronic configuration being intact. Crystal data: In0.272Ti2Nb6Cl13.728O4.272, space group C2/c (No.15), a = 12.679(2) Angstrom, b = 14.567(2) Angstrom, c = 12.632(3) Angstrom, beta = 95.26(2)degrees, Z = 4; Tl0.196Ti2Nb6Cl13.804O4.196, space group C2/c (no. 15), a = 12.732(1) Angstrom, b = 14.607(2) Angstrom, c = 12.662(2) Angstrom, beta = 95.28(1)degrees, Z = 4.