M-type barium hexaferrites (Ba1-xLaxFe12O19) were prepared by the liquid phase epitaxial (LPE) method, in which Ba2+ was substituted by La3+. The Faraday rotation effect of materials in the frequency range of 0.5–0.8 terahertz (THz) is studied by THz time-domain spectroscopy (THz-TDS). It was demonstrated that the M-type barium hexaferrites have a large Faraday rotation angle, and the Faraday rotation angle can be further enhanced by the substitution of La3+. For 500 µm thick film samples, the Faraday rotation angle exceeded 20° under the maximum measuring magnetic field of 400 mT. Moreover, the Faraday rotation angle is not saturated, and it will further increase with the increase of the magnetic field. At 0.8 THz, the Faraday rotation angle of the sample with x = 0 is 21.48°, for x = 0.05 which is 21.62°, and for x = 0.19 which is 28.38°. The Faraday rotation angle is enhanced by about 32%. By measuring the magnetic properties of the material, we found that the fundamental cause of the enhancement in the Faraday rotation angle lies in the increased saturation magnetization of the material after La3+ substitution. In the experiment, it was also found that the transmittance of the material to the THz wave decreased sharply with the increase of La substitution. For sample x = 0, the transmittance is as high as 60%. When the substitution amount of La is only x = 0.05, the transmittance decreases to about 55%. When the maximum substitution amount of La is x = 0.24, the transmittance of the material is only about 2%.