Time-resolved optical emission spectroscopy has been successfully employed to investigate the evolution of plasma produced by the interaction of IR- and visible-pulsed laser beams with a titanium target in ambient air at atmospheric pressure. The characterization of the plasma-assisted pulsed laser ablation of the titanium target is discussed in this study. The emission spectrum produced by the titanium plasma in the wavelength range 200–1,000 nm has been carefully investigated for different experimental conditions. Boltzmann plots have been used in the calculation of the excitation temperature employing Ti II spectral lines at 286.23, 321.71, 325.29, 348.36, and 351.08 nm; this set of lines was tested and proved to be suitable for the measurement of the plasma temperature. The obtained temperature is in good agreement with the one obtained from Ti II spectral lines previously suggested by Hermann et al. [J. Appl. Phys. 77, 2928–2936, 1995, 22]. Moreover, the Stark broadening method has been employed for electron density measurements. In this study, the Stark width of the Ti II spectral line at 350.49 nm was used.