In this article, we review the preparation methods of silica and silica hybrid materials, as well as their surface modification and application in liquid chromatography (LC). First we discuss the synthesis and properties of silica and silica hybrids. In the second part, we present the modification methods leading to their stationary phases. The current state of the art of the stationary phase's synthesis during silanization, hydrosilation, and coating is discussed. A detailed characterization of both native silica and its modifications is provided. The most common stationary phases for reversed‐phase, normal‐phase, and hydrophilic interaction LC are featured. Unconventional stationary phases, for example, with bonded cholesterol molecules, are also included. The potential applications of the described stationary phases are presented.