In this work, strontium hexaferrite (SrFe12O19) was prepared using two different methods, the solid-state reaction and the sol–gel pechini methods. In each case, the structural properties and microstructural features were analyzed in order to evaluate their influence on the photocatalytic activity of the strontium hexaferrite. In addition, the magnetic properties of each sample were also investigated. The analysis of the photocatalytic activity was done using methylene blue as a test dye. The results show that the fabrication method significantly impacts how the photocatalytic activity occurs. Firstly, the bandgap energy of the sample obtained by the solid-state reaction method turned out to be smaller than that obtained by the sol–gel pechini method. This behavior was attributed to the structural differences shown between the two samples. On the other hand, particle size also has a significant effect on photochemical reactions. However, smaller particle sizes make it difficult for photons to transport in the system, resulting in reduced photocatalytic activity. In this case, better results were obtained from the sample obtained from the solid-state reaction method.