Single-shot femtosecond laser induced breakdown spectroscopy (LIBS) has been shown to be an effective means of detecting heavy metal dopants in porous thin films. Traditional LIBS analysis of trace dopants in modern painted surfaces or TiO2 films is difficult due to the broad noisy spectra of the titanium constituent and interference due to the substrate material. Femtosecond laser pulses provide excellent ablation of the target material with little damage to the underlying substrate. In this study a Ti:sapphire femtosecond laser pulse operated at 800 and 266 nm wavelengths and an Nd:YAG nanosecond laser operated at 266 nm were used to ablate 0.15–15 μm films of TiO2 doped with varying amounts of MgO. This application shows excellent detection of Mg down to 60 ppm with little interference by the substrate material.