Magnetoplumbite barium hexaferrite (BaFe11.8Co0.2O19) is synthesised through sol-gel auto-combustion method under two pH conditions of precursor solutions (acidic i.e. pH < 1 and neutral i.e. pH = 7). The XRD analysis followed by Reitveld refinement indicates the formation of phase pure samples in both cases but the barium hexaferrite obtained from acidic precursor solution has smaller crystallite sizes. The Transmission Electron Microscopy (TEM) analysis followed by High Resolution Transmission Electron Microscopy (HRTEM) confirms a lower particle size of ∼20 nm for barium hexaferrite synthesised from acidic pH precursor solution. The shift in Raman peak (520-540 cm−1) by 20 cm−1, represents the whole structural block and further confirms the differences in the distribution of particle sizes due to the method of synthesis. The magnetic studies display a lower coercive field for the samples with smaller particle sizes. This is due to the crystalline size-induced microstrain that controls the magneto-crystalline anisotropy, shape anisotropy and stress anisotropy. The electromagnetic characterisation confirms broader absorption in the range of 8–18 GHz (X-band) with RL ≤ −7 db for the entire range for the samples with smaller particle sizes.