A new series of oxides Ca3-xBixCo4O9+delta, (x = 0.0-0.75) with Ca2Co2O5-type structures were synthesized, and their structures, electrical properties, Seebeck coefficients, and thermal conductivities were measured. The values of Seebeck coefficients of the new oxides are all positive, showing that they are p-type conductors. Both the electrical conductivity and Seebeck coefficients increase with the increasing Bi contents which can be attributed to the increase of carrier mobility due to the larger size of Bi ion. The electrical conductivity, Seebeck coefficient, and the calculated value of the power factor of Ca3-xBixCo4O9+delta (x = 0.5) are 105 S cm(-1), 160 mu V K-1, and 2.7 x 10(-4) W K-2 m(-1) at 700 degrees C, respectively. The thermal conductivity of Ca3-xBixCO4O9+delta (x = 0.5) at room temperature is 1.14 W m(-1) K-1 and increase slightly with the increasing temperature. At 700 degrees C, the figure of merit of Ca3-xBixCo4O9+delta (x = 0.5) is 2.0 x 10(-4) K-1.