A trigonal propeller-shaped hybrid polyoxometalate (POM) (NH₂Me₂)₃{[Nd(Mo₄O₁₃)(DMF)₄]₃(BTC)₂}·8DMF (1; BTC = 1,3,5-benzenetricarboxylate) has been synthesized and structurally characterized. The planar {Mo₄} segment is tailored from the precursor Lindqvist polyoxoanion [Mo₆O₁₉]²⁻ firstly, and plays a key role in the reassembly of 1. Furthermore, the magnetic studies reveal that 1 shows single-molecule magnet (SMM) behavior.