Honeycombed hierarchical ultramacroporous/mesoporous silica microspheres were prepared via the hydrolysis of TEOS in the oil water interface, with subsequent diffusion and gelation in the acidic water phase microdroplets with the assistance of a simple homemade microdevice. The diffusion of furfuryl alcohol (FA) also happened at a relatively high rate during the hydrolysis and diffusion of TEOS. Therefore, plenty of FA will be inside of the water microdroplets and form a decent number of polyfurfuryl alcohol (PFA) microparticles, thereby obtaining honeycombed hierarchical porosity silica microspheres with abundant ultramacroporous cavities and mesopores after calcination. It was found that the concentration of FA, residence time, and reaction temperature have significant effects on the porosity and pore size due to the influence on the diffusion rate and amount of FA in water-phase microdroplets. The honeycombed silica microspheres have obvious microscopic visible ultramacroporous cavities with the submicrometer cavity diameter as high as 85% porosity based on the rough overall volume of microsphere. N-2 adsorption-desorption isotherms show that the honeycombed hierarchical porosity silica microspheres have a high surface area of 602 m(2) g(-1), a mesopore volume of 0.77 cm(3)/g, and a mesopore porosity of 99.6% based on the total pore volume of N-2 adsorption desorption. On the basis of the experiment results, a rational formation process of the honeycombed hierarchical porosity silica microspheres was deduced.