Introduction E-scooters have made a place for themselves on urban roads as an affordable, easy-to-use and environmentally friendly method of transportation. However, and partly because of their road behaviors and safety outcomes, e-scooter users have started to represent a focus of attention for transport planners and policymakers. Aim The present systematic review aims to target and analyze the existing studies investigating the psychosocial characteristics of e-scooter riders, focusing on their behavioral and risk-related features. Methods For this systematic review, the PRISMA methodology was used, which allows for the selection of suitable papers based on the study topic, in accordance with a set of pre-defined criteria and a search algorithm. A total of 417 indexed articles were filtered, resulting in only 32 eligible original articles directly addressing the issue. WOS, Scopus, NCBI, Google Scholar, and APA databases were used to create and test search techniques. Results At the literature level, most of the existing studies are distributed in a few regions of the globe. At the user’s level, results show how e-scooters are most commonly used by young, highly educated, urban-dwelling males, usually for short trips. In regard to road behavior, individuals with the lowest degrees of risk perception remain more prone to engaging in risky road behaviors likely to increase their crash involvement. This might be worsened by the lack of normative e-scooter regulations (and their enforcement) in many countries, plus the marked absence of road training processes. As common limitations, it can be mentioned that 87.5% of these studies used self-report methods, while 59.4% had local coverage. Conclusions The findings of this systematic review endorse the growing need to develop and enforce traffic laws and training processes for e-scooter users. In addition, road safety education and training programs are highlighted by existing studies as potentially pertinent alternatives to increase risk perception, and reduce risky behaviors, road conflicts and crash likelihood among e-scooter riders.