Benzimidazole derivatives have garnered significant attention in medicinal chemistry owing to their versatile pharmacological properties, particularly their potent antimicrobial activity. This review comprehensively explores the advancements in the synthesis of benzimidazoles and their antimicrobial property evaluation from 2018 to 2024. Recent synthetic methodologies emphasize green chemistry approaches including solvent-free and catalyst-driven reactions, offering improved yields, selectivity, and environmental sustainability. Structural modifications, such as functionalization at positions 2 and 5/6 of the benzimidazole ring, were extensively investigated to enhance the antimicrobial efficacy against a broad spectrum of pathogens including multidrug-resistant bacterial and fungal strains. Furthermore, we elucidate the structure–activity relationships (SARs) of benzimidazole derivatives, enabling the rational design of highly potent antimicrobial agents. The mentioned period also witnessed the integration of hybrid molecules, wherein benzimidazoles were conjugated with other bioactive scaffolds to achieve synergistic antimicrobial effects.