Sugar cane biomass is a rich and powerful source of carbon atoms for renewable fuel generation. However, its efficient introduction into the standard refinery installation still a challenge. Recently, we have shown the possibility to produce gasoline compounds through refinery-friendly biocrudes obtained by one-pot hydrolysis-ketalization reaction of second-generation sugar cane biomass. Herein, we describe the development and validation of a liquid chromatography-triple quadruple mass Spectrometry (LC-MS/MS) method to quantify four carbohydrate-derived O-isopropylidene ketals present in biocrudes obtained by different reaction conditions and also the identification of six other compounds based on MS/MS fragmentation experiments. The validated method was selective; precise, accurate, and linear over the range of 012-25 mu g mL(-1), with correlation coefficient values higher than 0.99. The reaction carried out at 90 degrees C for 3 h resulted in a biocrude with 34.2% (w/w) of biomass conversion and 38.1% formation of the monitored O-isopropylidene ketals, with xylose diacetonide being the most abundant and rapidly formed compound. In addition, disateharides of pentose and pentose-hexose containing from one to three O-isopropylidene units have been identified. This LC-MS/MS analysis permitted a better understanding of the chemical composition of biocrudes and, therefore, could remarkably improve the possibility of tailor-made biocrudes in function of the regular refinery process.