The work attempted to develop a new kind of high temperature microwave absorption material. Dense Na3Zr1.9M0.1Si2PO11.9 (M = Ca2+, Ni2+, Mg2+, Co2+, Zn2+) and Na3Zr2-xZnxSi2PO12-x (x = 0.1, 0.2, 0.3, 0.4) ceramics were prepared by solid-state reactions for phase, microstructure characterization and dielectric properties, microwave absorption properties analysis. Results show that the complex permittivity increases in all the divalent-doped Na3Zr2Si2PO12 ceramics. Na3Zr1.8Zn0.2Si2PO11.8 ceramic exhibits the highest complex permittivity and optimum microwave absorption performance. The lowest reflection loss is -28.1 dB at 9.88 GHz and the bandwidth is 4.14 GHz (8.26–12.4 GHz) with a thickness of 2.1 mm. It indicates that Na3Zr2Si2PO12 ceramic can be chosen as a potential candidate of microwave absorption material and the performance can be enhanced by divalent doping strategy.