This article is aimed at providing a review of the progress made over the past decade in the preparation of polar monoliths for hydrophilic interaction LC (HILIC)/capillary electrochromatography (HI-CEC) and in the design of immuno-monoliths for immunoaffinity chromatography that are based on some of the polar monolith precursors used in HILIC/HI-CEC. In addition, this review article discusses some of the applications of polar monoliths by HILIC and HI-CEC, and the applications of immuno-monoliths. This article is by no means an exhaustive review of the literature; it is rather a survey of the recent progress made in the field with 83 references published in the past decade on the topics of HILIC and immunoaffinity chromatography monoliths.