The combination of p‐type NiOx and self‐assembled monolayers (SAMs) has recently emerged as an optimal structure for hole transport layer (HTL) structure in wide‐bandgap perovskite solar cells (WBG PSCs). However, the unique requirements for NiOx in this cascade HTL system differ significantly from those of neat NiOx. Specifically, the tendency of NiOx to agglomerate can lead to poor film morphology and inadequate interfacial contact with SAMs, resulting in significant open‐circuit voltage (Voc) loss in PSCs. Herein, these issues are addressed by incorporating sodium hexametaphosphate (SHMP) into NiOx ink. This approach enhances the dispersibility of NiOx nanoparticles, improving the morphology and conductivity of the NiOx films through interactions between the P = O and P‐O groups and Ni ions. Additionally, SHMP promotes better contact between the NiOx and Me‐4PACz interface by increasing the number of hydroxyl groups on the uniform surface of NiOx films. Consequently, a high power conversion efficiency (PCE) of 21.02% is achieved for WBG (1.79 eV) PSCs with the smallest relative Voc loss of 24.69%. The encapsulated devices exhibit excellent stability under high humidity and elevated temperatures. Furthermore, when combined with Sn‐Pb narrow‐bandgap perovskite, a PCE of 27.66% is attained for the 2‐terminal tandem solar cells (TSCs).