The first actinyl phosphinimine complexes have been synthesized and, in the case of uranium, exhibit strong U-N interactions. Competition reactions clearly demonstrate a surprising preference for R3P=NH ligands over R3P=O in the system [AnO(2)Cl(2)(R3PX)(2)] (An = U-VI, Np-VI; R = Ph, Cy; X = 0, NH). Spectroscopic evidence for N-donor coordination to [NPO2](2+) in solution indicates chemical similarities to the [UO2](2+) moiety.