Laser-induced breakdown spectroscopy (LIBS) enables the direct measurement of cell electrolyte concentrations. The utility of LIBS spectra in biomarker studies is limited because these studies rarely consider basic physical principles. The aim of this study was to test the suitability of LIBS spectra as an analytical method for biomarker assays and to evaluate the composition of electrolyte elements in human biomaterial. LIBS as an analytical method was evaluated by establishing KCl calibration curves to demonstrate linearity, by the correct identification of emission lines with corresponding reference spectra, and by the feasibility to use LIBS in human biomaterial, analyzing striated muscle tissues from the oral regions of two patients. Lorentzian peak fit and peak area calculations resulted in better linearity and reduced shot-to-shot variance. Correct quantitative measurement allowed for differentiation of human biomaterial between patients, and determination of the concentration ratios of main electrolytes within human tissue. The clinical significance of LIBS spectra should be evaluated using peak area rather than peak intensity. LIBS might be a promising tool for analyzing a small group of living cells. Due to linearity, specificity and robustness of the proposed analytical method, LIBS could be a component of future biomarker studies.