The thermoelectrical properties of α and γ phases of NaxCo2O4 having different amounts of Na were evaluated. The γ NaxCo2O4 samples were synthesized by thermal decomposition in a metal-citric acid compound, and the α NaxCo2O4 samples were synthesized by self-flux processing. Dense bulk ceramics were fabricated using spark plasma sintering (SPS), and the sintered samples were of high density and highly oriented. The thermoelectrical properties showed that γ NaxCo2O4 had higher electrical conductivity and lower thermal conductivity compared with α NaxCo2O4 and that α NaxCo2O4 had a larger Seebeck coefficient. These results show that γ NaxCo2O4 has a larger power factor and dimensionless figure of merit, ZT, than α NaxCo2O4.