We report the formation of novel microstructured SiCNO films with smooth, egg-shaped, and strawberry-like spheres by a block copolymer micellar-templating approach, in which polyvinylsilazne (PVSZ) swelled F127 micelles are allowed to evaporate at different temperatures over the different periods of time, followed by the cross-linking at 140 degrees C and the pyrolysis at 800 degrees C. The evolution process of smooth, egg-shaped, and strawberry-like spheres in the microstructured SiCNO films is observed by controlling the evaporation temperature and time of the multistep thermal treatment. The SiCNO films with varied internal microstructures have potential for harsh environment applications including high-temperature sensors and high oxidation/corrosion resistance.