Environmental pollution is increasingly recognized as a significant contributor to skin and scalp damage. Oral supplementation with a specific blend of four standardized botanical extracts (Rosmarinus officinalis, Lippia citriodora, Olea europaea leaf, and Sophora japonica) has been previously demonstrated to enhance skin health in individuals exposed to high environmental stress. Thus, it might represent a convenient strategy to also improve their scalp health aspect, particularly in subjects with sensitive scalps. To support these effects, a 12-week double-blind, randomized, placebo-controlled trial was performed in 66 women working outdoors in urban areas with high particulate matter (PM) levels and taking 250 mg of the botanical blend daily. Product efficacy was measured as follows: skin antioxidant status (FRAP); skin and scalp moisturization (corneometer), transepidermal water loss (tewameter), and oiliness (sebumeter); skin radiance and colour (spectrophotometer), elasticity and firmness (cutometer) and wrinkle depth (image analysis); and scalp clinical evaluation. Despite constant exposure to increased levels of PM, the tested product positively influenced all monitored parameters compared to both baseline and the placebo-treated group, in as early as 4 weeks. At the end of the study, key improvements included increased skin FRAP (21.9%), moisturization (9.5%), radiance (24.9%) and reduced wrinkle depth (−16.5%), dark spot pigmentation (−26.2%), and skin oiliness (−19.3%). For the scalp, moisturization increased (14.1%), TEWL decreased (−13.8%), and sebum content reduced by 16.2%. Additionally, 71% of subjects with sensitive scalps experienced reduced redness. These findings highlight the extensive benefits of the ingredient, expanding its application beyond conventional skin treatments to also alleviate scalp issues.