The α-MoO3 ceramics were prepared by uniaxial pressing and sintering of MoO3 powder at 650 oC and their structure, microstructure, densification and sintering and microwave dielectric properties were investigated. The sintering temperature of α-MoO3 was optimized based on the best densification and microwave dielectric properties. After sintering at 650 oC the relative permittivity was found to be 6.6 and the quality factor was 41,000 GHz at 11.3 GHz. The full-width half-maximum of the A1g Raman mode of bulk α-MoO3 at different sintering temperatures correlated well with the Qf values. Moreover, the sintered samples showed a temperature coefficient of the resonant frequency of -25 ppm/oC in the temperature range from -40 to 85 oC and they exhibited a very low coefficient of thermal expansion of ±4 ppm/oC. These microwave dielectric properties of α-MoO3 will be of great benefit in future MoO3 based materials and their applications.