The oxygen permeation flux of Ce0.9Gd0.1O1.95-δ (CGO)-based oxygen transport membranes under oxidizing conditions is limited by the electronic conductivity of the material. This work aims to enhance the bulk ambipolar conductivity of CGO by partial substitution of Ce with the redox active element Pr. A series of compositions of PrxGd0.1Ce0.9-xO1.95-δ (x = 0, 0.02, 0.05, 0.08, 0.15, 0.25, 0.3 and 0.4) was prepared by solid state reaction. X-ray powder diffraction (XPD) indicates that Pr is completely dissolved in the fluorite structure up to 40 at.%. Pronounced nonlinear thermal expansion behavior was observed as a function of temperature, due to the simultaneous contributions of both thermal and chemical expansion. The electronic and ionic conductivities were measured as a function of temperature and oxygen partial pressure. Within the range from 10 to 15 at.% Pr, a drastic drop of the activation energy of the hole mobility and an abrupt increase of the hole conductivity at low temperature was observed. The behavior could be rationalized by a simple percolation model. Oxygen permeation fluxes through disk shaped samples fed with air on one side and N2 on the other side were also measured. The oxygen flux through Pr0.05Gd0.1Ce0.85O1.95-δ was higher than that for CGO by one order of magnitude owing to the enhanced electronic conductivity albeit the flux is still limited by the electronic conductivity. In terms of the electronic and ionic conductivity, the estimated maximum oxygen permeation flux of a 10 μm Pr0.4Gd0.1Ce0.9O1.95-δ -based membrane exceeds 10 Nml cm−2 min−1 at 900°C under a small oxygen potential gradient (0.21/10−3 bar) which is promising for use in oxygen production and in oxy-fuel combustion. Also the material may be well applicable to SOFC/SOEC composite electrodes where mixed conductivity is also desirable.