Two new three-dimensional metal–organic frameworks, [H2N(CH3)2]2[Zn(btec)]·DMF (1, H4btec=1,2,4,5-benzenetetracarboxylate acid) and [H2N(CH3)2][ZnLi(btec)]·DMF (2), have been solvothermally synthesized and structurally characterized by single crystal X-ray diffraction. Compound 1 based on μ4-btec features an anionic homometallic framework with 4-connected pts topology. Compound 2 is a heterometallic organic framework with rare (4, 4, 8)-connected network topology, which can be considered as constitute of a Li-btec (pts) net and a Zn-btec net. Moreover, the luminescent properties of two compounds are investigated in the solid state at room temperature. [ABSTRACT FROM AUTHOR]