Na4Zr2Si3O12 (NZS) ceramic particles have been prepared by sol-gel, alkoxide pyrolysis, aqueous solution and mist pyrolysis techniques using metal alkoxides. Powder XRD results showed that Na2ZrSi2O7 or Na2ZrSiO5 was eliminated with the main NZS Phase. The difference of the elimination phase and the firing-temperature dependence of their XRD S/N ratios reflected the features of NZS formation processes, which were dominated by the precursor polymer size and the residual alkyl group content. The mist pyrolysis NZS has shown the highest conductivity among four kinds of prepared NZS. It is probable that alkyl group elimination, which mainly takes place simultaneously with NZS crystallization at 800-degrees-C, would promote to create a dominant conduction path along the grain boundary.