Laser Induced Plasma Spectroscopy (LIPS or LIBS) is an alternative elemental analysis technology based on the optical emission spectra of the plasma produced by the interaction of high‐power laser with gas, solid and liquid. The increasing popularity of this technique is due to the ease of the experimental set‐up and to the wide fiexibility in the investigated material that does not need any pre‐treatment of the sample before the analysis. In this work, Laser Induced Breakdown Spectroscopy (LIBS) is used to determine the composition of titanium oxide film produced by anodized of Ti6Al4V alloy. We have used Ti lines in the spectral region between 470–520 nm to determine temperature of the plasma generated on anodized surface of Ti6Al4V alloy for temperature determination by Boltzmann plot method. In order to measure the content of oxygen and titanium ratio on the surface the alloy, we have used the oxygen lines 777.194, 777.417 and 777.539 nm, and titanium lines 780.597 and 782.491 nm observed in an ambient of argon. We have determined the best conditions of electro‐deposition, observing the intensity of the oxygen lines. Finally, we report the possibilities for the determination of the coating chemical composition using LIBS.