Mesoporous microparticles have the potential to be used in various fields, such as energy generation, sensing, and the environmental field. Recently, the process of making homogeneous microparticles in an economical and environmentally friendly way has gained much attention. Herein, rectangular mesoporous microblocks of various designs are produced by manipulating the fragmentation of colloidal films consisting of micropyramids while controlling the notch angles of pyramidal edges. During calcination of the colloidal films, cracks are generated in the valleys of micropyramids acting as notches, and the angle of notches can be controlled by the prepattern underneath the micropyramids. By changing the location of notches with sharp angles, the shape of microblocks can be controlled with excellent uniformity. After detaching the microblocks from substrates, mesoporous microparticles of various sizes with multiple functions are easily produced. This study demonstrates anti‐counterfeiting functions by encoding the rotation angles of rectangular microblocks of various sizes. In addition, the mesoporous microparticles can be utilized for separating desired chemicals mixed with chemicals of different charges. The method of fabricating size‐tunable functionalized mesoporous microblocks can be a platform technology to prepare special films and catalysts and for environmental applications.