Treatment of zinc(II) acetate with a ditopic (bis-tridentate) thiocarbazone {H2L, bis(pyridine-2-aldehyde) thiocarbazone} as a principal building block and potassium thiocyanate as a source of auxiliary ligand resulted in the self-assembly generation of a novel heterometallic Zn(II)/K(I) metal–organic framework (MOF) formulated as [Zn2(L)K2(µ2-H2O)2(µ2-SCN)4]n (1). It was isolated as a microcrystalline solid and fully characterized, including by single crystal X-ray diffraction. Crystal structure of 1 reveals a very intricate 3D framework assembled from the [Zn2L]2+ and [K2(µ2-H2O)2]2+ secondary building units (SBUs) and multiple µ2-thiocyanate linkers. Topological analysis of the simplified underlying net of 1 disclosed a binodal 4,8-connected framework with the flu (fluorite) topology. Synthesis, characterization, structural and topological features, as well as Hirshfeld surface analysis are discussed in the present study.