The aim of the study was to determine Ca addition to the flour by using laser-induced breakdown spectroscopy (LIBS) as a quick and simple multi-elemental spectroscopy method. Different amounts of CaCO3-added wheat flour were analyzed using LIBS to determine Ca content and Ca/K ratio, which is used for discrimination of natural and Ca-added flour. LIBS spectra were quantitatively evaluated with partial least square (PLS) method as a multivariate data analysis method to eliminate the matrix effect. Ca and Ca/K calibration graphs of PLS method showed good linearity with coefficient of determinations (R (2)) 0.999. Limit of detection values for Ca and Ca/K analysis were calculated as 25.9 ppm and 0.013, respectively. Furthermore, the results were found to be consistent with the data obtained from atomic absorption spectroscopy method as a reference method for flour samples.