Abstract: | Two luminescent metal‐organic frameworks (LMOFs), namely, Cd2(DDCPB) · (DMF)2 · H2O]n (CHD‐ 1 ) and Zn2(DDCPB) · (DMA)2]n · n(DMA) (CHD‐ 2 ), were solvothermally constructed, which present structural diversity. Single crystal X‐ray diffraction analysis indicates that they consist of Cd2(μ2‐O)2(κ‐O)2] building units (for CHD‐ 1 ), Zn2(κ‐O)6] building units (for CHD‐ 2 ), which are further linked by multicarboxylate H4DDCPB to construct microporous frameworks. Remarkably, both CHD‐ 1 and 2 exhibit highly efficient luminescent sensing for environmentally relevant Cu2+ ions through luminescence quenching. Theoretical and experimental calculations indicate that the luminescent quenching can be attributes to the donor‐acceptor electron transfer between the MOFs and analytes. This work indicates that CHD‐ 1 and 2 could be taken as a potential candidate for developing multifunctional luminescence sensors. |