The activity concentrations of 222Rn were measured in 53 public water supplies of underground (50) and surface (3) origin, and the relation of such with five geological units where these supplies are located, in the central Ecuadorian Andes, was also explored. These units supply drinking water to 10 cities, located between the 1500 and 3120 m.a.s.l. The experimental setup consisted of the RAD7 radon detector and the RAD H2O degassing system. The 222Rn levels measured in groundwater ranged from 0.53 to 14.78 Bq/L while surface waters did not indicate detectable radon levels. The radon concentrations were below the parametric value of 100 Bq/L for water intended for human consumption, recommended by the European Atomic Energy Community (EURATOM) in its Directive 2013/51, and the alternative maximum contamination level (AMCL) of 150 Bq/L, proposed by the Environmental Protection Agency (EPA). The Pisayambo Volcanic unit, mapped as intermediate volcaniclastic to felsic deposits, presented a mean radon concentration higher than the other geological units and lithologies (9.58 ± 3.04 Bq/L). The Cunupogyo well (11.36 ± 0.48 Bq/L) presented a radon concentration more than 70% higher than the neighboring springs, which may be explained by its proximity to the Pallatanga geological fault. The maximum annual effective doses, by cities, due to the ingestion and inhalation of radon, ranged from 0.010 to 0.108 mSv and from 0.008 to 0.091 mSv, respectively; therefore, these waters do not represent a risk to the health of the population. In addition, a correlation was observed between the activity concentration of 222Rn and the activity concentration of the parent 226Ra in samples collected from some springs.