A laser induced breakdown spectroscopy experiment was carried out using Nd∶YAG laser in air, and time-resolved spectra were measured. Based on local thermodynamic equilibrium assumption, a method used to simulate LIBS spectra is proposed. A LIBS spectrum of air in the wavelength range of 700~900 nm was simulated using this method. A good agreement between experiment and simulation was obtained, and moreover, the relative concentrations of the N, O and Ar in air were obtained.