In article number 2004843, Guangliang Chen, Jun Huang, Changsheng Song, and co‐workers demonstrate that Mulberry‐like Ni12P5‐Ni4Nb5P4 nanocrystals with rich heterointerfaces and phase edges are successfully fabricated on carbon cloth, which is enabled by intentional defect creation by atmospheric pressure dielectric barrier discharge plasma (PCC). The obtained Ni12P5‐Ni4Nb5P4/PCC electrocatalyst maintains spectacular catalytic activity at high current density region (>j615) for H2 evolution, which outperforms the industry‐relevant benchmark Pt/C/PCC catalyst.