This review article intends to explore the versatility in the formation of pyrrole‐fused quinone/naphthoquinone derivatives described in literature from 2008 to 2024. It deals with the multitude of paths to its synthesis from a variety of precursors using both metal‐ and metal‐free catalytic systems and their potential applications. This article also documented several bioactive cores accommodating indoloquinone and its analog. Noteworthy, mitomycin A acts as excellent medicine for variety of cancer treatment and its analog EO‐9 is under clinical trial. Here we present the synthesis of natural products zyzzyanone A, murrayaquinones B and murrayaquinones A, indolequinone‐based naloxone prodrugs exiguamine A and (NQO1)‐targeted prodrugs for hypoxia specific activation, antibiotic uthamycin B and its analog, indolequinone fused with ursolic acid (a triterpenoid rich in many Chinese medicines), which is a vital scaffold for the preparation of novel anticancer agent. Indoloquinone‐fused with ursolic acid (a triterpenoid rich in many Chinese medicines) is a vital scaffold for the preparation of novel anticancer agent. Recent synthesis of two cyanobacterial metabolites Calothrixins A and B has also been documented. This article also discusses the synthesis of intermediate, from where lymphostin alkaloid can be developed. Lamellarin D natural product can be easily prepared by the developed strategy.