Two kinds of novel double-headed 2-pyrrolidone derivatives (DHNRPs) were designed for efficient recovery of UO22+ from HNO3 (aq) and its separation from tetravalent metal ions (M4+). The DHNRPs bearing butylene or p-xylylene bridging moiety have successfully precipitated sparingly soluble [UO2(NO3)(2)(DHNRP)](n), while these ligands do not allow formation of any deposits of M4+ (M = Th, U, Zr). As other DHNRPs we reported previously afford sparingly soluble crystalline precipitates of both UO22+ and M4+ (M = U, Th, Np, and probably Pu), separation/co-precipitation of UO22+ from/with these tetravalent actinides can be achieved by employing appropriate molecular structure of DHNRPs.