This book introduces the fascinating world of self-assembly in mesoporous ordered silica films. Beginning from a single droplet, it guides the reader, in a step-by-step learning process, how to obtain and control ordered porous mesophases in thin films by varying only the precursor chemistry and the process. It explains, in great detail, how order control is achieved through chemical design and post-deposition processing, the latter of which is a unique property in materials science. The book places a special focus on silica, whose particularly complex chemistry enables order control over a range of different length scales. This book is suitable for students and researchers in the fields of sol-gel or colloidal chemistry and interested in the topics of self-assembly and mesoporous phases.