Group 3 and rare-earth triflate-complexes M(OTf)(2)(bdmpza) {M = Sc (1(Sc)), Y (1(Y)), La (1(La)), Sm (1(Sm)), Eu (1(Eu)) OTf = SO3CF3} bearing the heteroscorpionate ligand bdmpza {bdmpza = bis(3,5-dimethyl-pyrazol-1-yl)acetate} have been synthesized and characterized, together with the yttrium and europium complexes M(OTf)(bdmpza)(2) {M = Y (2(Y)), Eu (2(Eu))}. The photoluminescent behavior of 2(Eu) has been investigated. The coordination mode of the [N,N,O]-donor in these complexes has been elucidated by DFT calculations. The cytotoxic effect of selected complexes and of the free ligand toward HeLa cells has been evaluated.