The concentrations of vanadium and titanium elements in the steel samples were quantitatively analyzed by Laser-induced breakdown spectroscopy technique in the present paper. The lines of V (V Ⅰ: 440.85 nm) and Ti (Ti Ⅰ: 334.19 nm) were chosen as the quantitative analysis spectral lines, while spectral line of Fe (Fe Ⅰ: 438.35 nm) was chosen as the internal calibration line due to it being the matrix element. Then the calibration curves of V and Ti elements were established with basic calibration method and internal calibration method respectively to quantitatively analyze the concentrations of vanadium and titanium elements in steel. The experimental results showed that the fitting correlation coefficient (R2) of vanadium and titanium elements are 0.987 5 and 0.990 9 when using basic calibration method, and their maximum relative errors of measurement are 11.09% and 4% respectively; while the fitting correlation coefficient (R2) of vanadium and titanium elements reachs 0.995 2 and 0.992 1 respectively when using internal calibration method, at the same time, the relative errors of measurement for vanadium and titanium elements were decreased to be lower than 4%. The results of this study demonstrated that the concentration measurement of vanadium and titanium elements in the steel was more suitable with internal calibration method in laser-induced breakdown spectroscopy.