In the present work, the authors have investigated the binary system of (Bi2O3)(1-x)(Ho2O3)(x). For the stabilisation of the tetragonal type solid solution, small amounts of Ho2O3 were doped into the monoclinic Bi2O3 via solid state reactions in the stoichiometric range 0.01 <= x <= 0.1. The crystal formula of the formed solid solution was determined as Bi(III)(4-4x)Ho(II)(4x)O(6-2x)Vo((2+2x)) (where Vo is the oxide ion vacancy) according to the XRD and SEM microprobe results. In the crystal formula, stoichiometric values of x were 0.04 <= x <= 0.08, 0.03 <= x <= 0.09, 0.02 <= x <= 0.09 and 0.04 <= x <= 0.09 for annealing temperatures at 750, 800, 805 (quench) and 760 degrees C (quench) respectively. The four probe electrical conductivity measurements showed that the studied system had an oxide ionic type electrical conductivity behaviour, which is increased with increasing dopant concentration and temperature. The obtained solid electrolyte system has an oxygen non-stoichiometry characteristic, and it contains O2- vacancies, which have disordered arrangements in its tetragonal crystal structure. The increase in the amount of Ho2O3 doping and temperature causes an increasing degree of the disordering of oxygen vacancies and a decrease in the activation energy E-a.