Fecralloy coating layer with large surface area is suitable for use as a filter media for efficient removal of hot gaseous pollutants exhausted from combustion processes. For uniform preparation of a Fecralloy coating layer with large surface area and strong adhesion to substrate, electrospray coating and thermal treatment processes are experimentally optimized in this study. A nano-colloidal solution with 0.05 wt% Fecralloy nanoparticles is successfully prepared. Optimized electrospraying conditions are experimentally discovered to prepare a uniform coating layer of Fecralloy nanocolloidal solution on a substrate. Drying the electrospray coated Fecralloy nano-colloidal solution layer at 120°C and subsequent heating at 600°C are the best post-treatment for enhancing the adhesion force and surface roughness of the Fecralloy coating layer on a substrate. An electrospray coating system, consisting of several multi-groove nozzles, is also experimentally confirmed as a reasonable device for uniform coating of Fecralloy nano-colloid on a large area substrate.