Over the past few decades, research on heterogeneous catalysts, especially metal-free catalysts in industrial and research transformations, has intensified. Despite the obvious benefits of heterogeneous transition metal catalysts in quick substrate activation and acceleration of reactions, cost-effectiveness, high activity in harsh process conditions, ensuing pollution and sustainability issues are still some of the significant challenges. In this context, metal-free catalysts have been widely studied over the past few decades. The persistent question in the field of metal-free catalysts is their scalable design and the development with an acceptable economic approach and biocompatibility to achieve green and selective synthesis in the domain of industry and pharmaceuticals, as well as organic transformations. This article portrays recent developments in the exploitation of metal-free catalysts in organic synthesis.