The thermoelectric properties of W-substituted CaMn1-xWxO3-δ (x = 0.01, 0.03; 0.05) samples, prepared by soft chemistry, were investigated from 300 K to 1000 K and compared to Nb-substituted CaMn0.98Nb0.02O3-δ. All compositions exhibit both an increase in absolute Seebeck coefficient and electrical resistivity with temperature. Moreover, compared to the Nb-substituted sample, the thermal conductivity of the W-substituted samples was strongly reduced. This reduction is attributed to the nearly two times greater mass of tungsten. Consequently, a ZT of 0.19 was found in CaMn0.97W0.03O3-δ at 1000 K, which was larger than ZT exhibited by the 2% Nb-doped sample.