Optimally designed silver‐silicon (Ag‐Si) contacts based on silver (Ag) paste screen printing and the rapid sintering process, have been widely utilized in mainstream crystalline silicon solar cells, enabling to reduce contact resistance and high photo‐conversion efficiency. Ag powder is the largest conductive component in Ag paste, but its impact on the formation of Ag‐Si contacts lacks in‐depth research and comprehensive understanding. In this work, we demonstrated that the oxygen adsorption capacity of silver powders affected the formation of Ag‐Si contacts by enhancing the reactivity of Ag powders with glass frits, and had a significant effect on the performance of devices. The generation of Ag2O introduced by surface absorbed oxygen promoted the transformation of [TeO4] triangular bipyramidal into [TeO3] triangular pyramid, thus destroying the network structure of the glass frits. This structural decay accelerated the spreading of glass frits in the bulk, causing the glass frits to come into contact with SiNx layers earlier and facilitating the formation of the Ag‐Si contacts. This work not only provides a complete picture of the interaction between Ag powder and glass frits, but also a new direction to optimize the Ag‐Si contacts.This article is protected by copyright. All rights reserved.