© The Royal Society of Chemistry 2015. Stoichiometry and oxygen diffusion properties of La2-xSrxNiO4±δ with x = 0.2, 0.4, 0.6, and 0.8 prepared via a sol-gel method were investigated in this study. Iodometric titration and thermogravimetric analysis were used to determine the oxygen non-stoichiometry. Over the entire compositional range, the samples exhibit oxygen hyperstoichiometry with the minimum value δ = 0.14 at x = 0.4. Mixed effects of reduction of oxygen excess and increasing valence of Ni were found to serve as charge compensation mechanisms; the former dominated at a low level of substitution, x < 0.4, while the latter dominated at higher levels of Sr (0.4 < x < 0.8). The highest oxygen diffusion coefficient was found for the minimum amount of Sr substitution, x = 0.2, continuously decreasing with x until x = 0.6. An unusual increase in D∗ was observed when the Sr content increased up to x = 0.8.