We demonstrated 22 W LD-pumped high-power continuous-wave (CW) deep red laser operations at 718.5 and 720.8 nm based on an a-cut Pr3+:YLF crystal. The output power of both polarized directions reached the watt-level without output power saturation. A single wavelength laser operated at 720.8 nm in the π-polarized direction was achieved, with a high output power of 4.5 W and high slope efficiency of approximately 41.5%. To the best of our knowledge, under LD-pumped conditions, the laser output power and slope efficiency are the highest at 721 nm. By using a compact optical glass plate as an intracavity etalon, we suppressed the π-polarized 720.8 nm laser emission. And σ-polarized single-wavelength laser emission at 718.5 nm was achieved, with a maximum output power of 1.45 W and a slope efficiency of approximately 17.8%. This is the first time that we have achieved the σ-polarized laser emission at 718.5 nm generated by Pr3+:YLF lasers.