In this work, we report the synthesis of silver decamolybdate, Ag₆Mo₁₀O₃₃, nanostructure by a simple mechanohemical process followed by calcination treatment using acetamide as driving agent. Morphological study by scanning electron microscopy (SEM) images revealed bundles of rods grown closely together with an average diameter of 92 nm for Ag₆Mo₁₀O₃₃ sample. Ni-substituted Ag₆Mo₁₀O₃₃ compound was prepared via introducing nickel cation to precursor system in mechanical milling step. The particle size decreased to 87 nm by incorporating nickel units in substituted polymolybdate. It was concluded that the suitable selection of reagents can direct solid phase reaction towards producing nanostructured products. This technique is easy and simple for preparation of various mixed metal oxides without using any solvents and or complex procedures. In addition, the photocatalytic activity of the prepared products was studied on the removal of 4-nitro phenol (4-NP) as organic pollutant from water. The obtained results were also discussed in detail.