In this manuscript, the time-resolved laser-induced breakdown spectroscopy (LIBS) on tungsten target in air and the coexistence of LTE among atoms and ions as well as the fulfillment of optically thin plasma condition are reported. The laser-induced plasma (LIP) of tungsten is generated by focusing the second harmonic of a Q-switched Nd:YAG laser of pulse width ~7 ns and repetition rate of 1 Hz on the tungsten target. The temporal evolution of LIP of tungsten is recorded at four different incident laser fluences of 60, 120, 180, and 270 J/cm2. The several atomic and singly ionized lines of tungsten are identified in LIP. For the estimation of plasma temperature via the Boltzmann plot, the transitions at 430.7, 449.4, 468.0, 484.3, 505.3, and 524.2 nm of Atomic transition of tungsten (WI) and that of the ionic transitions, First Ionic transition of Tungsten (WII) at 251.0, 272.9, and 357.2 nm are selected. The electron density is estimated using the Stark-broadened profile of WI line at 430.2 nm. The McWhirter criteria for the local thermodynamic equilibrium (LTE) condition is verified in present experimental conditions as well as the relaxation time and diffusion length are estimated to take into account the transient and inhomogeneous nature of the plasma. The optically thin plasma condition is studied by assessing the experimental intensity ratio of atomic lines and compared with that of the theoretical intensity ratio (branching ratio). The signal to noise ratio (SNR) is also obtained as a function of time with respect to laser pulse and incident laser fluence. All these observations indicate that the spectra should be recorded within the temporal window of 1–3.5 µs with respect to laser pulse where the plasma can be treated as optically thin as well as under LTE simultaneously along with the large SNR.