The effects of Li2CO3-V2O5 (LV) co-doped on the sinterability, phase compositions and microwave dielectric properties of Mg4Nb2O9-CaTiO3 composite ceramics have been investigated. The phase compositions and microstructure were analyzed using X-ray diffraction, energy dispersive X-ray analysis and scanning electron microscopy techniques. The densification sintering temperature is lowed from 1275oC to 1200oC with an amount LV addition. For the specimen with 1.5 wt% LV addition sintered at 1200oC for 5 h exhibited dielectric properties: εr=23, Q·f=24 000 GHz (at 7.7GHz ), τf =1.0 ppm/oC. These properties were correlated with the formation of non-stoichiometric compound Mg4(Nb1-xTix)2O9-δ.