In recent years, reverse phase-dispersive liquid-liquid microextraction (RP-DLLME) has emerged as a highly versatile and efficient sample preparation in analytical chemistry. This miniaturized extraction method distinguishes itself by employing a hydrophilic extractant solvent dispersed in a predominantly hydrophobic sample matrix, which is the inverse of conventional DLLME approaches. RP-DLLME offers numerous advantages, including significant solvent reduction, high enrichment factors, short extraction times, simplicity, cost-effectiveness, and minimal environmental impact, aligning with the principles of Green Analytical Chemistry (GAC). Additionally, the RP-DLLME demonstrated remarkable versatility for the analysis of complex matrices with high organic content, such as edible oils, lubricating oils, and petroleum-derived. This review provides a comprehensive an overview of the concepts, fundamentals, advantages, limitations, and advances of RP-DLLME in various samples for the determination of elemental and organic compounds, covering works published up to 2025.