This review focuses on the application of various silica hydride stationary phases under conditions that enable the advantages of reversed-phase, aqueous normal phase and organic normal phase selectivity to be gained. Here, an overview is given related to the characteristics of the most frequently used silica hydride stationary phases, including those involving short n-alkyl chain (Diamond Hydride), phenyl, octyl, octadecyl and cholesterol phases. Explanations are provided to account for their unique retention properties, which enable their versatile application in the analysis of biological and pharmaceutical samples under conditions significantly different to those employed with conventional silica-based reversed phase or hydrophilic interaction stationary phase materials.