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We presented the possible mechanisms regarding to formation of nano ZnO and ZnO/Zn nanocomposite by various polysaccharides as chelates. The same polysaccharide namely corn starch with different modification process led to the difference in the formation of final products. The results indicated surface interaction and the formation of intermediates mainly control the structure of final products. This study has revealed that the selected modification process for polysaccharides is an appropriate method to synthesize the formation of ZnO nanomaterials of particular interest with controlled composition. Our findings shed light on the optimization of preparation conditions for obtaining the desired final products of interest. Keywords: Polysaccharides, Mechanism, Nano ZnO, ZnO/Zn nanocomposite