This chapter describes the most representative contributions to the field of sol–gel hybrid materials for optics and electro‐optics. Hybrid coatings with potential applications as smart windows, radiation protection coatings, coatings for optical lenses, photochromic and electrochromic materials, nonlinear materials, refractive and photorefractive, sensors, waveguides, optical filters and absorbers, reflecting and AR coatings, optical biofilms, magneto‐optical materials, UV protection coatings, and space materials can be found among the research lines in this field. Besides the objective of novel applications, the characterization of their physicochemical properties and the study of the molecular interactions of the dopants with the embedding surfaces of the hybrid matrices have been deeply investigated. Examples covering various aspects of the optical sol–gel materials and the contributions describing recent progresses and interdisciplinary approaches to materials with novel properties are summarized.