This study presents a comprehensive investigation of the structural and magnetic properties of La_0.8Sr_0.2Mn_0.8Co_0.2O₃ (LS1, LS2 and LS3) compounds synthesized via the sol–gel method at different gelation temperatures through X-ray diffraction and different magnetic measurement techniques. The Rietveld refinement demonstrated that all samples exhibit a rhombohedral perovskite structure with the RC space group. Their magnetic behavior, characterized through magnetization measurements, hysteresis loops, and Arrot plots, demonstrates a ferromagnetic–paramagnetic transition with notable soft ferromagnetic characteristics. The samples also demonstrate second-order magnetic transitions, short-range magnetic order and the presence of both ferromagnetic and antiferromagnetic contributions. AC magnetic susceptibility measurements, allowing the investigation of the magnetic dynamics of the samples, shows that the Vogel–Fulcher and the Conventional Critical Slowing Down models are the most appropriate for describing the dynamic behavior, confirming the spin-glass nature of the compounds and the presence of medium to strong interaction between magnetic nanoparticles. The influence of gelation temperature in the magnetocaloric effect of the compounds was proven and LS1, synthesized at the lowest gelation temperature (70 °C), exhibits the higher magnetic entropy change (|ΔS_max| = 3.25 J kg⁻¹ K⁻¹ and RCP = 209.83 J kg⁻¹ at 5 T). For a better evaluation of the magnetocaloric efficiency, the temperature average entropy change (TEC) parameter was calculated for all three samples and LS1 showed the highest value (TEC (LS1) ∼3.2 J kg⁻¹ K⁻¹ for ΔT_H–C = 10 K and ΔH = 5 T).