The plume expansion dynamics strongly affects the growth and the chemistry of pulsed laser deposited thin films. The interaction with the background gas determines the kinetic energy of the species impinging on the substrate, their angular broadening, the plasma chemistry, and eventually the cations stoichiometric ratio in oxide films. Here, we exploit two-dimensional, spectrally resolved plume imaging to characterize the diverse effects of the oxygen background pressure on the expansion dynamics of La, Ga, and LaO species during pulsed laser deposition of LaGaO3. The propagation of the ablated species towards the substrate is studied for background oxygen pressures ranging from high vacuum up to ≈10−1 mbar. Our experimental results show specie-dependent effects of the background gas on the angular distribution of the precursors within the plume. These findings suggest that even in the presence of a stoichiometric ablation and of a globally stoichiometric plume, cations off-stoichiometry can take place in the forefront portion of the plume impinging on the substrate. We show that such effect can be compensated by a proper choice of process parameters.