Substituted barium ferrites powders with Ti4+-M2+ (M = Co, Zn, Sn) cationic mixtures were prepared by a sol-gel route. The materials were heat-treated in the range 925–1000 °C and characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM) and vibrating sample magnetometry (VSM). The results showed that the effect of the substitution, x was to lower the coercivity (Hc), owing to the decrease of the magnetocrystalline anisotropy of the magnetoplumbite structure of the BaM. In this regard Sn-Ti substitutions tended to decrease Hc more rapidly than Zn-Ti and Ti-Co substitutions, in that order. Regarding the saturation magnetization (Ms), Zn-Ti mixtures showed slightly better Ms than Ti-Co substitutions; however, the Sn-Ti showed a more marked decrease as x increased. As revealed by SEM, the effect of the heat-treatment temperature was to increase the volume of multi-domain particles, following a Hc decrease due to grain coarsening. Contrarily, as a result of the improved crystallinity of the samples, as observed from the XRD peaks, Ms enhancement was recorded. Crystallite sizes decreased below 100 nm as x increased, although it was also dependent on the cationic mixture. In this respect Sn-Ti substitutions needed higher treatment temperatures to yield materials with adequate crystallinity and phase constitution.