We find that single inorganic polyoxomolybdate molecule can self-assemble with beta-CD molecule forming a novel beta-CD/MoxOyn- inclusion complex under rapid crystallization conditions. Experiments have proven that it is rapid crystallization of beta-CD that leads to formation of surplus beta-CD nuclei, which immediately include single inorganic molecule into them forming this inclusion complex. We believe that this research opens a new field of inorganic species/beta-CD inclusion complex and also opens new way to synthesize inorganic semiconductor nanomaterials by using beta-CD as template via a green and efficient route. Crown Copyright (C) 2012 Published by Elsevier B.V. All rights reserved.