Polymeric and porous ceramic micro- and nanospheres were prepared by a simple solidification process with a liquid preceramic polymer in an oil-water-emulsification process. The system was composed of a water-crosslinkable poly(methoxymethylsiloxane) as the preceramic polymer and a linear hydroxyl-terminated poly(dimethylsiloxane) as a source for in situ water generation. Emulsification followed by subsequent curing was carried out via an ultrasonic treatment in the presence of surfactants and a crosslinking active organometallic catalyst. The rheological behavior of the polymeric base system was characterized and the crosslinking behavior was investigated as a function of catalyst concentration and temperature. Effects of composition and processing parameters such as energy input and type and concentration of the surfactant were determined with respect to the microstructure and particle size distribution of the obtained polymeric spheres. The particle diameters of the as-synthesized spheres were mainly in the sub-micron range. Pyrolysis was performed in argon atmosphere at 1073.15 K resulting in the formation of amorphous ceramics under shape retention.