Due to its low cost, over the past decades, biosorption technology has been extensively carried out to treat heavy metal-laden wastewater using biosorbents. Recent studies on heavy metal biosorption mechanisms and the simulation of mathematical modeling on the biosorption process have enhanced scientific understanding about the binding between target metal cations and the functional group on different surfaces of biomasses as a biosorbent. However, so far, none have provided an overview of mechanistic studies on heavy metal removal from aqueous solutions using inexpensive biosorbents. To close this knowledge gap, this article discusses the applicability of the surface complexation (SC) model for biosorption of a target pollutant. Insightful ideas and directions of future research in wastewater treatment using digital technologies are also presented. It was conclusive from a literature survey of 115 articles (1987–2023) that Aspergillus niger, Penicillium chrysogenum, and Rhizopus nigricans represent biomaterials that have substantial adsorption capacities, up to 200 mg of Au(I)/g, 142 mg of Th/g, and 166 mg of Pb(II)/g, respectively. The metal-binding mechanisms involved include ion exchange, surface complexation, and micro-precipitation. Ion exchange is the only mechanisms that play key roles in sequestering heavy metal using fungal cells with chitin and chitosan. X-ray energy dispersion (XED) and scanning electron microscopy (SEM) analysis were used to evaluate biosorption mechanisms of the inorganic pollutants using physico-chemical characterization on the cell surfaces of the biomass. As metal removal by the biosorbent is affected by its surface properties, surface complexation also occurs. The affinity of the surface complexation depends on the type of functional groups such as phosphate, carboxyl, and amine.