Results of thermo-electric power (S) and electrical resistivity (r) measurements are reported on NaxCoO2 compounds with x = 1.0, 0.7 and 0.6. These are single-phase compounds crystallizing in the hexagonal structure (space group P63/mmc) at room temperature. Thermo-electric power values at 300K (S300K) are, 80mV/K, 39mV/K and 37mV/K for x = 1.0, 0.7 and 0.6 samples, respectively. The samples with x=0.7 and 1.0 are metallic down to 5 K, while the x = 0.6 sample is semiconducting. The value of r300K for x = 1.0 sample is ~0.895 mW-cm and the power factor (S2/r) is = 7.04 x 10-3 W/mK2 which qualifies it as a good thermo-electric material. In x =1.0 sample, S(T) is positive throughout 300-5K temperature range and decreases monotonically to zero as temperature T= 0. In contrast, S(T) of x = 0.7 and 0.6 samples changes sign and shows negative values between 90 K and 16 K before approaching zero as T = 0. Anomalous S(T) behavior of x = 0.6 and 0.7 samples, which are coincidentally the precursor materials to the reported superconductivity in this class of materials, indicates a dramatic change in the electronic structure of these compounds on lowering the Na content.