The types of dopants lead to distinctive microstructural evolution behavior and physical properties in materials. In this study, the effect of stoichiometric and non-stoichiometric Mn modification, namely Pb(Mn1/3Nb2/3)O3 (PMnN) and MnO2, on the microstructure and properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 (PYN-PZT) piezoelectric ceramics are systematically investigated. It was found that stoichiometric PMnN modification inhibits the grain growth while non-stoichiometric MnO2 modification promotes it, and thus the former yields stronger high-power characteristics (higher internal bias field Ei and larger mechanical quality factor Qm) than the latter. Specifically, with an equivalent amount of Mn modification (2 mol%), PMnN and MnO2 modification PYN-PZT ceramics exhibit significantly different values for average grain size (1.21 μm vs. 14.12 μm), Ei (8.5 kV/cm vs. 5 kV/cm), and Qm (2376 vs.1134). To further evaluate high-power performance, the vibration velocity v of these two modified PYN-PZT under high driving conditions was measured. Under an AC electric field of 3.5 V/mm, the PYN-PZT+6PMnN ceramics exhibit a v of up to 0.95 m s−1, larger than both MnO2-doped PYN-PZT (0.72 m s−1) and unmodified PYN-PZT ceramics (0.1 m s−1), and far outperformance than both PZT-4 and PZT-8 ceramics. Furthermore, to elucidate the origin of the exceptional high-power performance of PMnN-modified PYN-PZT, we performed phase-field simulations revealing a pinning effect of the grain boundary on domain wall motion. Consequently, the small grain size (high grain boundary density) in PMnN-modified PYN-PZT exhibits a strong pinning effect, resulting in a large Qm and outstanding high-power performance.