Layered CaTaN2 and MgTa2N3 and cubic Mg2Ta2N4 were prepared by direct solid state reaction from the binary nitrides Ta3N5 and A3N2 (A: Mg, Ca). CaTaN2 showed a slight Ca deficiency (0.11 moles per formula), and a monoclinic distortion from previously reported R3̅m symmetry, with space group C2/m and cell parameters a = 5.4011(2), b = 3.1434(1), c = 5.9464(2) Å and β = 107.91(3)°. Ca2+ and Mg2+ deintercalation was investigated in the three compounds both chemically and electrochemically. No significant Mg2+ extraction could be inferred for MgTa2N3 and Mg2Ta2N4, neither after reaction with NO2BF4 nor after electrochemical oxidation at 100 °C in alkyl carbonate electrolytes. Rietveld refinement of the X-ray powder diffraction pattern of chemically oxidized Ca0.89TaN2 indicates a decrease of the Ca content to 0.34 concomitant to the disappearance of the monoclinic distortion and expansion of the interlayer space from 5.658 to 5.762 Å, space group R3̅m and cell parameters a = 3.1103(1) and c = 17.287(1) Å. Deintercalation in this compound was also achieved electrochemically at 100 °C. Results of density functional theory calculations seem to indicate that reaction mechanisms for CaTaN2 oxidation additional and/or alternative to deintercalation are taking place, which is likely related to the loss of crystallinity observed upon oxidation and the irreversibility of the process.