Enhanced Oil Recovery (EOR) operations in complex reservoirs frequently contend with persistent crude oil-water emulsions, necessitating the use of chemical breakers to separate phases and improve hydrocarbon recovery. Traditional emulsion breaker technologies often suffer from limited efficacy under reservoir-specific conditions such as high salinity, extreme temperatures, and heterogeneous fluid compositions. This paper presents a comprehensive technical review of next-generation microemulsion breaker technologies, emphasizing their chemical architectures, performance mechanisms, and field-reported capabilities. Building upon the theoretical principles of microemulsion systems—comprising surfactants, co-surfactants, oil, and water phases—the study explores classification schemes (Winsor types), interfacial phenomena, and thermodynamic stability factors that influence efficacy in EOR applications. The review further evaluates emerging trends in high-performance surfactants, nano-enhanced systems, and stimuli-responsive formulations that exhibit superior emulsion breaking efficiency and environmental compatibility. By analyzing laboratory-to-field transition metrics and published field performance indicators, the study identifies critical enablers and deployment barriers. Finally, it outlines future research pathways, including AI-guided formulation development and multifunctional chemical design, that hold promise for scalable, efficient, and sustainable EOR implementations.