Emission spectrum of the laser‐induced plasma plume is obtained during KrF excimer laser ablation of graphite in argon and hydrogen gas mixture for deposition of diamond‐like films. Bands of C2and CN molecules dominate the spectrum while weak CI, CII, and H&agr;lines are also observed. From the emission intensities, molecular vibrational temperature is calculated to be (12–15)×103K, and concentrations are estimated to be N(C2)=5×1014cm−3and N(CN)=2×1014cm−3.