Personal chemical exposure assessment is necessary to determine the frequency and magnitude of individual chemical exposures, especially since chemicals present in everyday environments may lead to adverse health outcomes. In the last decade, silicone wristbands have emerged as a new chemical exposure assessment tool and have since been utilized for assessing personal exposure to a wide range of chemicals in a variety of populations. Silicone wristbands can be powerful tools for quantifying personal exposure to chemical mixtures in a single sample, associating exposure with health outcomes, and potentially overcoming some of the challenges associated with quantifying the chemical exposome. However, as their popularity grows, it is crucial that they are used in the appropriate context and within the limits of the technology. This review serves as a guide for researchers interested in utilizing silicone wristbands as a personal exposure assessment tool. Along with briefly discussing the passive sampling theory behind silicone wristbands, this review performs an in-depth comparison of wristbands to other common exposure assessment tools, including biomarkers of exposure measured in biospecimens, and evaluates their utility in exposure assessments and epidemiological studies. Finally, this review includes recommendations for utilizing silicone wristbands to evaluate personal chemical exposure and provides suggestions on what research is needed to recognize silicone wristbands as a premier chemical exposure assessment tool.