The present study analyzed the presence of the principal volatile compounds of the BTEX type (benzene, toluene, ethylbenzene, and xylene [o-, m- and p-xylene]) in samples of water from wells located at residences and gas stations in two Amazonian towns—Tracuateua and Augusto Corrêa—in the Amazon region of northern Brazil. This innovative study is extremely relevant to the Amazonian towns surveyed, given that they lack systematic policies for the environmental control of gas stations and any municipal regulations on the quality of water destined for human consumption. A combination of mass spectrometry (MS) and gas chromatography (CG) techniques was applied to analyze these contaminants in 150 samples of local groundwater collected between 2020 and 2024. One of the four BTEX compounds (toluene) was identified in seven of the samples collected (4.66% of the total) at concentrations of 0.14–2.10 µg L−1. The concentrations of contaminants were low, in general. None of the water samples analyzed here presented any critical loss of water quality for human consumption according to the Brazilian legislation concerning BTEX concentrations. Neither of the two towns surveyed in the present study has remediation programs for environmental contamination. The GC-MS approach produced satisfactory results for the assessment of the contamination of underground water reserves by gas stations in both study towns. Further research (e.g., geophysical methods) will be necessary to determine the source of the contamination and its connection with the levels of toluene identified in the underground water sampled in these Amazonian towns.