AbstractNa‐ion batteries based on abundant and sustainable materials might become one of the leading alternative technologies especially suitable for large‐scale stationary storage. Various (mixed)phosphate framework materials are attracting much interest mainly due to their high structural stability and diversity. In this study, we report on the successful synthesis of mixed phosphate‐pyrophosphate Na₇V₄(PO₄)(P₂O₇)₄, Na₄Fe₃(PO₄)₂P₂O₇, and Na₄Mn₃(PO₄)₂P₂O₇. The electrochemical properties of these materials are comprehensively characterized in different organic and aqueous electrolytes. The findings reveal that Na₇V₄(PO₄)(P₂O₇)₄ and Na₄Fe₃(PO₄)₂P₂O₇ exhibit very good cycling performance and rate capability in organic solvent‐based electrolytes. However, their performance deteriorates significantly even in ‘water‐in‐salt’ aqueous electrolytes due to the rapid electrochemical degradation. Na₄Mn₃(PO₄)₂P₂O₇ demonstrates limited electrochemical activity in organic electrolytes and virtually no activity in ‘water‐in‐salt’ electrolytes, likely due to degradation processes resulting in blocking interphasial layers on electrode particles. These results underscore the need for further research to optimize the performance of these materials and identify potential strategies for enhancing their stability and activity in different electrolytes.