Cobalt element plays an important role for the properties of magnetism and thermology in steels. In this work, laser-induced breakdown spectroscopy combined with laser-induced fluorescence (LIBS-LIF) was studied to selectively enhance the intensities of Co lines. Two states of Co atoms were resonantly excited by a wavelength-tunable laser. LIBS-LIF with ground-state atom excitation (LIBS-LIFG) and LIBS-LIF with excited-state atom excitation (LIBS-LIFE) were compared. The results show that LIBS-LIFG has analytical performance with LoD of 0.82 μg/g, R2 of 0.982, RMSECV of 86 μg/g, and RE of 9.27%, which are much better than conventional LIBS and LIBS-LIFE. This work provided LIBS-LIFG as a capable approach for determining trace Co element in the steel industry.