Disease breathomics is gaining importance nowadays due to its usefulness as non-invasive early cancer detection. Mass spectrometry (MS) technique is often used for analysis of volatile organic compounds (VOCs) associated with cancer in the exhaled breath but a long-standing challenge is the uncertainty in mass peak annotation for potential volatile biomarkers. This work describes a cross-platform MS strategy employing selected-ion flow tube mass spectrometry (SIFT-MS), high resolution gas chromatography-mass spectrometry (GC-MS) retrofitted with electron ionisation (EI) and GC-MS retrofitted with positive chemical ionisation (PCI) as orthogonal analytical approaches in order to provide facile identification of the oxygenated VOCs from breath of cancer patients. In addition, water infusion was applied as novel efficient PCI reagent in breathomics analysis, depicting unique diagnostic ions M+ or [M-17]+ for VOC identification. Identity confirmation of breath VOCs was deduced using the proposed multi-platform workflow, which reveals variation in breath oxygenated VOC composition of oesophageal-gastric (OG) cancer patients with dominantly ketones, followed by aldehydes, alcohols, acids and phenols in decreasing order of relative abundance. Accurate VOC identification provided by cross-platform approach would be valuable for the refinement of diagnostic VOC models and the understanding of molecular drivers of VOC production.