Fruta-do-lobo (Solanum lycocarpum St. Hill) is an underutilized native fruit commonly found in the Brazilian Cerrado, very known due to the presence of glycoalkaloids. In this work we evaluated the biochemical changes on carbohydrates, phenolic and alkaloids during ripening of fruta-do-lobo using chromatographic and spectrometric techniques. During ripening, we observed an increase in glucose, fructose and sucrose, while oligosaccharides levels varied. Chlorogenic acid isomers represented 80% of the identified phenolic compounds in unripe stage, but they reduced during ripening, resulting in predominance of p-coumaroylquinic acid (peel and pulp) and 1-O-sinapoyl-glucoside (seeds). Statistical analysis shows that the unripe fractions were richer in alkaloids compounds, which were the most important for antioxidant activity. Molecular network analysis summarizes the compound changes during ripening, especially regarding the alkaloid compounds, with a reduction of around 85% of solamargine abundance. These data show that fruta-do-lobo can presents different chemical compositions due their ripening stage providing support for future research aimed to the application of these compounds in glycemia control or uses of their extracts with higher content of alkaloids compounds.