In this study, macroporous ceramic particles were synthesized by emulsion-assisted self-assembly with or without the use of sacrificial templates. Sodium silicate was employed as an economical precursor for the synthesis, and hence industry-scale application of the particles can be expected with control over particle size distribution. After the removal of sodium from sodium silicate using an ion-exchange resin, the resultant aqueous silicic acid solution was emulsified in a continuous oil phase to form tiny droplets that act as micro-reactors for template-free synthesis of porous silica particles. The crumpling and folding of the thin silica shell inside the emulsion during heating resulted in the formation of porous particles without the use of templates. The particles were spherical with a number of irregular macropores. Macroporous silica particles with spherical cavities were also synthesized using polystyrene nanospheres as sacrificial templates and silicic acid as a precursor of silica. In a demonstrative application, the porous particles were used as coating materials in the fabrication of water-repellent surfaces by lotus effect, indicating that the particles can be potentially applied to self-cleaning surfaces.