Prussian blue (PB) analogues are representatives of the coordination materials and have shown important contributions in the field of Electrocatalysis and molecular magnets. These materials exhibit unique electrochemical and magnetic behaviors depending on their constituents and ratios of transition metal ions in specific geometrical orientation. In‐situ generated PB nanoparticles were prepared by using a mixture of 3‐Aminopropyltrimethoxysilane and potassium ferricyanide that was allowed to react with three different moieties; (a) tetrahydrofuran (THF), (b) cyclohexanone, and (c) ferrous sulphate, resulting in the formation of soluble PB. An excellent transparent organically‐modified sol‐gel glass (ORMOSIL) films encapsulating PB nanoparticles were formed in each cases. The particles have been examined by atomic force microscopy (AFM) and transmission electron microscopy (TEM) and have shown excellent varying electrochemical properties. The novel finding on these materials on the electrocatalysis of dopamine and hydrogen peroxide based on electrochemical measurements is reported in this communication.