The oxidative stability and the oxygen permeability of oil-loaded capsules were investigated by Electron Spin Resonance (ESR). The capsules were produced by spray-drying or electrospraying in the monoaxial or coaxial configuration using glucose syrup as the encapsulating agent. ESR-spin trapping results showed that electrosprayed capsules oxidized faster and during the early stages of incubation, irrespective of the emitter configuration (monoaxial or coaxial), when compared to those produced by spray-drying. Furthermore, ESR oximetry showed that oxygen inside the spray-dried capsules reached equilibrium with the surrounding atmosphere significantly slower than the monoaxially electrosprayed capsules (i.e., ∼2h and ∼10 min, respectively). These findings have been attributed to the larger particle size of the spray-dried capsules influencing the oxygen diffusion area (i.e., lower surface-to-volume ratio) and diffusion path (i.e., thicker encapsulating wall for a fixed oil load). Together, the lower oxygen uptake reported for the spray-dried capsules correlated well with their higher oxidative stability.