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Single crystal of Li2Zn2(MoO4)3 has been grown from a flux of Li2MoO4 by the top-seeded solution-growth method, and its structure was refined by the Rietveld method. It belongs to the orthorhombic system, space group Pnma with a=5.1114, b=10.4906 and c=17.6172(A). Good agreement between the experimental and calculated profile (Rp=6.69%, Rwp=9.73% and Rexp=6.58%) was reached.