Bi26Mo10O69, i.e. [Bi12O14](2)[Bi2Mo10O41] is a purr oxide anion conductor. It can be considered as the first member of the bismuth-based mono-dimensional oxide anion conductors with a skeleton built upon [Bi12O14](proportional to) columns. In order to modulate its electrical performances, attempts of substitutions in bismuth sites and molybdenum sites were performed. Several dopants have been checked: (i) Pb-II, Ca-II, Sr-II, Ba-II for bismuth sires, (ii) P-V, W-VI for molybdenum sites. Six solid solutions, formulated Bi26-xMexMo10O69-0.5x with Me = Pb, Ca, Sr, Ba, Bi26Mo10-xPxO69-0.5x and Bi26Mo10-xWxO69, were characterized. The substitution ratio in bismuth site is systematically limited to two, indicating that the bismuth atoms located in the columns were not affected. In a general way, introduction of oxygen vacancy in the parent compound led to a small decrease of its performances. However the electrical performances of these materials were considerably enhanced by partial substitution for molybdenum with tungsten, giving rise to very attractive properties.