Novel 3D coordination polymer {NdBi(EDTA)(NO3)2(H2O)7,22} 1 with unprecedented type of coordination of EDTA ligand has been synthesised. It represents the first structurally characterised heterometallic lanthanide–bismuth polyaminocarboxylate and the first example of the Bi(EDTA)− moiety with coordinated NO3− anions. One of the two NO3− anions is disordered in two resolvable positions with the 0.74:0.26 occupancy factors. The major component can be formulated as [(H2O)5Nd(μ4-EDTA)Bi(NO3)2]·3H2O (1a), while the minor component can be described by [(NO3)(H2O)3Nd(μ4-EDTA)Bi(NO3)]·2H2O (1b).