<p>Homemade alcohol-related deaths are a significant public health issue which is often overlooked. Methanol, which can be produced through fermentation or deliberately added by the brewers to the beverages, has been reported as the leading cause of most deaths around the world. Botswana has not been spared as cases of death following the consumption of homemade alcoholic beverages remain high; unfortunately, most of these deaths have never been investigated for methanol content. We hereby present, for the first time, a study involving the investigation of eight different samples of Botswana homemade alcoholic beverages for methanol content. A brief history of the samples revealed that they were obtained from local brewers around the country as evidence of deaths related to alcohol consumption. A liquid–liquid extraction gas chromatography mass spectrometry method for the detection and quantification of methanol in the homemade alcoholic beverages was optimized for the extraction of methanol using ethyl acetate and validated for accuracy, precision, repeatability, selectivity, linearity, limit of detection, limit of quantification, and stability. The validated method showed good linearity with correlation coefficient (<i>R</i>²) of 0.996. It was found to be precise with %RSD values ≤ 5%. Repeatability was acceptable with %RSD values ≤ 5%. Also, percentage recoveries were within 100% with lower LOD and LOQ values. After successful validation, all eight samples from the Botswana Police were analyzed. Methanol was detected and quantified in five samples being T16, T42, T46, T50 and T55 at concentrations ranging from 0.04 to 1.6% v/v. The non-carcinogenic risk assessment revealed that methanol values in these samples were around the safety level of 1 (0.783–1.57) when using the guidelines of the United States Environmental Protection Agency (USEPA).</p>