Between 1564 and 1810, nearly 17,000 metric tons of mercury (Hg) vapor was released to the environment during cinnabar refining in the small town of Huancavelica, Peru. The present study characterizes individual exposure to mercury using total and speciated Hg from residential samples, total Hg in hair, and self-reported questionnaire data regarding factors influencing exposure (e.g., frequency of fish consumption, occupation). Total Hg concentrations in hair from 118 participants ranged from 0.10 to 3.6 µg/g, similar to concentrations found in the USA and lower than concentrations in other Hg-exposed populations around the world. Pearson's correlation coefficients for data in this study suggest that there is a positive correlation between concentrations of total Hg in hair and concentrations of total Hg in adobe bricks, dirt floors, and surface dust; however, these correlations are not statistically significant. Results of a one-way analysis of variance (ANOVA) identified that total Hg concentrations in hair were significantly related to gender (p < 0.001), living in a neighborhood where smelters were previously located (p = 0.021), smoking status (p = 0.003), frequency of house cleaning (p = 0.019), and frequency of fish consumption (p = 0.046). These results highlight the need for further studies to better characterize Hg exposure in Huancavelica, particularly as related to residential contamination. A comprehensive analysis of residential Hg contamination and exposure in Huancavelica will guide the development and implementation of mitigation and remediation strategies in the community to reduce potential health risks from residential Hg exposure.