Polyoxovanadates (III) are important class of polyoxometalates in molecular magnetism field, and particularly the systems which contain vanadium(III) centers. To date, only very few highly reduced vanadium polynuclear complexes were reported, which remains a significant challenge to synthesize novel polyoxovanadates, owing to the characteristics of easily oxidized vanadium(III). Herein, two unprecedented petaloid chiral octanuclear polyoxovanadates, L- and D-[H2N(CH3)(2)](12.5)(H3N(CH2)(2)NH3)-(H3O)(1.5)(V-III mu(2)-OH)(8)(SO4)(16)center dot 2H(2)O (L-, D-V-8), have been successfully obtained by solvothermal method without any chiral auxiliary. Both L- and D-V-8 compounds contain the motif eight-membered ring (V mu(2)-O)(8)(SO4)(16) constituted of three different chiral entangled loops with the V atoms as nodes. Bond valence calculation (BVC) analysis indicates that all the V ions existed in L, D-V-8 are +3 value. The magnetic behavior of compounds indicated ferromagnetic coupling between vanadium(III) ions. To our knowledge, it is the first chiral highly reduced polyoxovanadates that exhibit excellent ferromagnetism.