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Alginate is a natural marine biopolymer that has been widely used in biomedical applications, but research on its use as an endodontic material is still sparse in the literature. This pioneer review aims to summarize the emerging roles of alginate and to outline its prospective applications as a core biomaterial in endodontics. Ten electronic databases and five textbooks were used to perform a search of English-language literature on the use of alginate in endodontics published between January 1980 and June 2022. The risk of bias (RoB) of each included study was assessed using the Office of Health Assessment and Translation (OHAT) tool. Subsequently, studies were categorized into three tiers to represent the overall risk. Qualitative analysis was performed, and the articles were sorted into different thematic categories. An initial search yielded a total of 1491 articles, but only 13 articles were chosen. For most domains, all the studies were rated with 'probably low' or 'definitely low' RoB, except for domains 2 and 6. All included studies fall in the Tier 1 category and were either in vitro, in vivo, or ex vivo. Four thematic categories were identified: endodontic regeneration, intracanal medicament, filing material, and chelating agent. Based on the available evidence, alginate has emerged as a cell carrier and scaffold in regenerative endodontics, a microcapsule delivery system for intracanal medicaments, a chelating agent reinforcing material, and a root canal sealer. More well-designed experiments and clinical trials are needed to warrant the promising advent of this hydrogel-based biomaterial. [ABSTRACT FROM AUTHOR]