The introduction of the article provides a historical overview of nickel-catalyzed cross-couplings, highlighting the evolution from early transition metals like nickel (Ni) to more advanced catalysts such as palladium (Pd) and platinum (Pt). The text emphasizes the advantages of using phenol- and enol-derived electrophiles, which are readily available and can be accessed from natural sources or easily prepared from other aromatic species. These electrophiles offer the benefit of oxygenation on the aromatic ring, allowing for the introduction of additional substituents through various pathways, including electrophilic aromatic substitution. The article also discusses the economic benefits of using Ni over Pd and Pt, as Ni is a more cost-effective and versatile reagent. The scope of the review covers the historical development, current state-of-the-art, and future prospects of Ni-catalyzed homocoupling, cross-coupling, and functionalization of carbon-oxygen (C-O) bonds. The review is organized by the type of phenol-derived electrophile used, and it includes detailed sections on the mechanisms and applications of Ni-catalyzed reactions. A significant portion of the article focuses on the homocoupling of aryl and vinyl sulfonates and sulfates, detailing the historical progress and key findings in this area. Early work by Semmelhack and others on the use of Ni0 complexes for homocoupling aryl halides and pseudohalides is discussed, along with the development of more efficient catalysts and reaction conditions. The role of reducing agents like Zn0 and hydride-mediated reduction in enhancing the catalytic activity is highlighted. The article also explores the scope and reactivity of Ni0-catalyzed homocoupling of aryl sulfonates, including the synthesis of various polyaromatic compounds and polymers. Overall, the article provides a comprehensive overview of the advancements and challenges in nickel-catalyzed cross-couplings, emphasizing the versatility and economic advantages of using Ni as a catalyst.The introduction of the article provides a historical overview of nickel-catalyzed cross-couplings, highlighting the evolution from early transition metals like nickel (Ni) to more advanced catalysts such as palladium (Pd) and platinum (Pt). The text emphasizes the advantages of using phenol- and enol-derived electrophiles, which are readily available and can be accessed from natural sources or easily prepared from other aromatic species. These electrophiles offer the benefit of oxygenation on the aromatic ring, allowing for the introduction of additional substituents through various pathways, including electrophilic aromatic substitution. The article also discusses the economic benefits of using Ni over Pd and Pt, as Ni is a more cost-effective and versatile reagent. The scope of the review covers the historical development, current state-of-the-art, and future prospects of Ni-catalyzed homocoupling, cross-coupling, and functionalization of carbon-oxygen (C-O) bonds. The review is organized by the type of phenol-derived electrophile used, and it includes detailed sections on the mechanisms and applications of Ni-catalyzed reactions. A significant portion of the article focuses on the homocoupling of aryl and vinyl sulfonates and sulfates, detailing the historical progress and key findings in this area. Early work by Semmelhack and others on the use of Ni0 complexes for homocoupling aryl halides and pseudohalides is discussed, along with the development of more efficient catalysts and reaction conditions. The role of reducing agents like Zn0 and hydride-mediated reduction in enhancing the catalytic activity is highlighted. The article also explores the scope and reactivity of Ni0-catalyzed homocoupling of aryl sulfonates, including the synthesis of various polyaromatic compounds and polymers. Overall, the article provides a comprehensive overview of the advancements and challenges in nickel-catalyzed cross-couplings, emphasizing the versatility and economic advantages of using Ni as a catalyst.