Lipid oxidation remains a concern leading to deterioration of the organoleptic quality in processed goods, but it should be minimized by considering changes in the structural properties of foods. The present work investigates the effect of glass transition temperature on the oxidation of linoleic acid at different concentrations of κ-carrageenan/glucose syrup. A combination of 0.5, 1, 2 and 3% (w/w) κ-carrageenan and 82.5, 82, 81, 80% (w/w) glucose syrup were mixed with 1.5% (w/w) linoleic acid and 0.5% (w/w) lecithin to prepare samples with a total solid content of 85% (w/w). Physicochemical properties of these mixtures were recorded using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). This was followed by estimation of the mechanical (Tgm) and calorimetric (Tgc) glass transition temperatures using small deformation dynamic oscillation in-shear and modulated differential scanning calorimetry (MDSC). The linoleic acid oxidation in the condensed polysaccharide/co-solute system was evaluated by monitoring the accumulation of hydroperoxide (ROOH) with UV–vis spectroscopy over a wide temperature range (−25 to 0 °C). The oxidation phase was modelled following a sigmoidal kinetic model indicating initiation and propagation stages of lipid oxidation. ROOH production increased as a function of time and temperature. The structural relaxation of the polymeric matrix influenced the oxidation rate at the initiation stage. At the propagation phase, Tgm appears to control the rate of ROOH formation and decomposition in all preparations, as compared to Tgc, an outcome that makes the former an important concept of quality control.