The enhancement of natural radioactivity in groundwater, specifically in natural mineral water, is related to the lithological formations through which water bodies or courses pass. Although natural mineral waters are exempt from monitoring for radioactive substances according to Council Directive 2013/51/EURATOM, this study focuses on the radiological characterization of natural mineral water under Spanish Royal Decree 3/2023. The water studied was taken from Catalan aquifers with different lithological characteristics (sedimentary, metamorphic or granitic) and is sold on local markets. Moreover, radiological data on the water was correlated with its lithological origin and the health risk for different age groups was assessed. Our results showed that of the 26 natural mineral waters studied, 10 exceeded gross alpha screening value (100 mBq/L), all from granitic aquifers. Further research on natural individual radionuclides was conducted on these ten samples. 234U and 238U were at around 1100–1600 mBq/L. In addition, 210Pb was found in two samples, which also presented the highest 226Ra activity, associated with granitic bedrock and the presence of 210Po. The annual effective dose was 179.0 µSv/year and 145.9 µSv/year, exceeding 100 µSv/year mainly due to the contribution of 210Pb > 234,238U > 210Po > 226Ra, in this order. After assessing the lifetime cancer risk, these two samples were determined not to pose a health risk due to ingestion. Although no radiological monitoring is required for natural mineral water, further surveillance is recommendable.