Na3V2(PO4)3 (NVP) has gained a lot of attention due to its remarkable properties, such as its robust crystal structure, cycle life, rate capabilities, and so on. Nevertheless, NVP goes through a substantial decrease in its rate capability at low temperatures, which limits its practical applications. In this study, the performance of NVP at low, room, and high temperatures during cycling is thoroughly investigated using synchrotron operando X-ray diffraction. The (de)-insertion of two sodium ions from Na3V2(PO4)3 to Na1V2(PO4)3 is appeared to occur via two intermediate phases (Na2V2(PO4)3 and Na1.64V2(PO4)3). The Na1.64V2(PO4)3 phase which is observed for the first-time during operando XRD measurements of NVP, exhibited limited stability at high temperatures. The increase in the quantity of these intermediate phases from high to low temperatures, especially at high C-rates could be anticipated to be one of the contributing factors of poor rate capabilities of NVP at low temperatures. This study encourages the exploration of suitable strategies to enhance the performance of NVP at low temperatures and high C-rates.