The unregulated oil exploitation in the Northern Ecuadorian Amazon Region (NEAR), mainly from 1964 to the 90's, led to toxic compounds largely released into the environment. A large majority of people living in the Amazon region have no access to drinking water distribution systems and collects water from rain, wells or small streams. The concentrations of major ions, trace elements, PAHs (polycyclic aromatic hydrocarbons) and BTEX (benzene, toluene, ethylbenzene, xylenes) were analyzed in different water sources to evaluate the impacts of oil extraction and refining. Samples were taken from the NEAR and around the main refinery of the country (Esmeraldas Oil Refinery/State Oil Company of Ecuador) and were compared with domestic waters from the Southern region, not affected by petroleum activities. In most of the samples, microbiological analysis revealed a high level of coliforms representing significant health risks. All measured chemical compounds in waters were in line with national and international guidelines, except for manganese, zinc and aluminum. In several deep-water wells, close to oil camps, toluene concentrations were higher than the natural background while PAHs concentrations never exceeded individually 2 ng·L−1. Water ingestion represented 99% of the total exposure pathways for carcinogenic and non-carcinogenic elements (mainly zinc) in adults and children, while 20% to 49% of the Total Cancer Risk was caused by arsenic concentrations. The health index (HI) indicates acceptable chronic effects for domestic use according the US-EPA thresholds. Nevertheless, these limits do not consider the cocktail effects of metallic and organic compounds. Furthermore, they do not include the social determinants of human exposure, such as socio-economic living conditions or vulnerability. Most (72%) of interviewed families knew sanitary risks but a discrepancy was observed between knowledge and action: religious beliefs, cultural patterns, information sources, experience and emotions play an important role front to exposure.