One of the most crucial attributes of synthetic organic chemistry is to design organic reactions under the facets of green chemistry for the sustainable production of chemicals. Thus, due to the intensified environmental and safety concern, the need for new technologies for conducting chemical transformation has grown. In this regard, there is enormous interest in the use of heterogeneous catalysts as they generally avoid the generation of waste, require fewer toxic reagents, as well as entail easier separation and recycling of the catalyst. α,β-Unsaturated acids have been widely used in various industrial applications and have been identified as one of the most promising chemicals obtained via the Knoevenagel condensation reaction. This review aims to discuss the most pertinent heterogeneous catalytic systems such as zeolites, mesoporous silica, ionic liquids, metal oxides, and graphitic carbon nitride-based catalysts in the Knoevenagel reaction. Ultimately, this review focuses not only on the catalyst but also provides an overall idea and guide for the preparation of new catalysts with outstanding properties by looking at the chemical and engineering aspects such as the reaction conditions and the mechanisms.