Investigation of luminescent materials with efficient photoluminescence (PL) and mechanoluminescence (ML) is significant for the development of both basic theories and industrial applications for new light sources, pressure sensors, and information security. In this study, we obtain a pair of isomorphic europium(Eu)³⁺-containing coordination polymers (CPs), namely, [Eu(tfpd)₃(phen)]_n (1) and [Eu(tfpd)₃(bipy)]_n (2) (tfpd = 4,4,4-trifluoro-4-pyridyl-1,3-diketonate, phen = 1,10-phenanthroline, bipy = 2,2′-bipyridine), which exhibit novel helical chain-like structures that can be extended to 3D supramolecular networks through moderate interchain interactions. The thermostable CPs simultaneously exhibit strong photoluminescence (PL) emissions with high quantum yields and excellent mechanoluminescence (ML) activity with an unusual anti-thermal quenching effect. Careful analyses of the CP crystal structures and …