The inventors developed a novel and reliable top-down RPLC-MS method for the absolute quantification of the most relevant isoforms of HSA using an internal standard and two different quantitative approaches: deconvolution and XIC. They have demonstrated its successful validation and implementation on plasma samples corresponding to different stages of liver pathologies. In addition, using myoglobin as an internal standard and for mass recalibration, inventors have improved mass accuracy, which is a critical metric in HSA isoforms identification.