(1) Background: Widespread personal care product (PCP) use can expose individuals to endocrine-disrupting chemicals (EDCs) associated with adverse health outcomes. This study investigated the association between harm perceptions and hair-product-purchasing behaviors in adults enrolled in a cross-sectional study. (2) Methods: Respondents rated their agreement with five PCP-related harm statements using a five-point Likert scale. Multivariable-adjusted logistic regression models were used to examine the associations between harm perceptions with hair-product-purchasing behaviors and hair product use (i.e., number of products used). (3) Results: Among 567 respondents (non-Hispanic White, 54.9%; non-Hispanic Black, 9.5%; Hispanic/Latinx, 10.1%; Asian American/Pacific Islander, 20.1%; and multiracial/other, 5.5%), stronger harm perceptions around PCP use were associated with potentially “safer” hair-product-purchasing behaviors. Respondents who strongly agreed that consumers should be concerned about the health effects of PCPs had more than fourfold increased odds of always/usually using healthy product apps (OR 4.10, 95% CI: 2.04–8.26); reading ingredient labels (OR 4.53, 95% CI: 2.99–6.87); and looking for natural, non-toxic, or eco-friendly product labels (OR 4.53, 95% CI: 2.99–6.88) when buying hair products. (4) Conclusions: Promoting environmental health literacy and raising awareness of potential PCP use-related harms might encourage healthier hair product use behaviors.