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Research suggests that ~60% of patients prescribed cardiovascular drugs do not take their medication correctly. The analysis of dried blood spot samples (DBS) by liquid chromatography-high resolution mass spectrometry (LC-HRMS) for assessing medication adherence to candidate therapeutic drugs used in cardiovascular therapy was investigated. Specificity using this analytical method was based on the measurement at the accurate mass to charge ratio of the target analyte. To evaluate the method 8mm discs were punched from each DBS and extracted followed by subjecting to LC-HRMS analysis. Trials on 6 commonly UK used cardiovascular drugs are reported demonstrating the ability of the system to detect the target analytes during the 24 hour repeat prescription cycle. Samples from volunteers with confirmed adherence were used to validate the response from the system as were samples from volunteers receiving no medication. No false positives were observed and adherence assessment for bisoprolol, ramipril, amlodipine, valsartan, doxasozin and simvastatin was demonstrated using the LC-HRMS method. Furthermore examples of incorrect adherence were identified.