Humans are exposed to numerous potentially harmful chemicals throughout their lifetime. Although many studies have addressed this issue, the data on chronic exposure is still lacking. Hence, there is a growing interest in methods and tools allowing to longitudinally track personal exposure to multiple chemicals via different routes. Since the seminal work by O’Connell et al. (2014), silicone wristbands (WBs) have been increasingly used to facilitate human exposure assessment, as using WBs as a wearable sampler offers new insights into measuring chemical risks involved in many ambient and occupational scenarios. However, the literature lacks a detailed overview regarding methodologies being used; a comprehensive comparison with other approaches of personal exposure assessment is needed as well. Therefore, the aim of this review is fourfold. First, we summarize hitherto conducted research that employed silicone WBs as personal passive samplers. Second, all pre-analytical and analytical steps used to obtain exposure data are discussed. Third, we compare main characteristics of WBs with key features of selected matrices used in exposure assessment, namely urine, blood, hand wipes, active air sampling, and settled dust. Finally, we discuss future needs of research employing silicone WBs. Our work shows a variety of possibilities, advantages, and caveats associated with employment of silicone WBs as personal passive samplers. Although further research is necessary, silicone WBs have already been proven valuable as a tool for longitudinal assessment of personal exposure.