The electrochemical energy conversion and storage devices have to be large to go through a new paradigm in which the huge power sources are required to handle kWh or MWh energies for highly efficient energy storage system and electric vehicles. Despite lithium ion batteries (LIBs) have been widely applied as major power sources for small portable electronic devices during several decades, they will no longer be so easy to use owing to high cost and limitation of lithium resources. Nowadays, sodium ion batteries (NIBs) have attracted increasing attention as alternative power sources to LIBs due to the abundant supply and low cost. In this regard, a lot of researchers have vigorously investigated the active materials for cathode and anode to utilize sodium ion battery. Additionally, developing new electrode materials with high specific capacity for excellent sodium ion storage properties is very desirable for high energy power sources. As an anode material, red phosphorus is very promising thanks to its high theoretical capacity (∼2600 mA h g^-1), however, it has several problematic issues of undesirable low cycle life from the large volume change during sodiation/desodiation and insufficient power density from the poor conductivity. We add Bi₂O₃ to phosphorous for reducing those failure modes of phosphorus for NIBs because Bi₂O₃ has high electronic conductivity and small volume changes during cycles. In this presentation, we tried to improve the electrochemical performances of phosphorus by introducing the composite material of bismuth oxide (Bi₂O₃)/phosphorus by controlling the nano-morphology via simple top down method of ball milling. The prepared sample was investigated by using XRD, SEM and TEM analyses to follow the sample morphology for anode of NIBs. It is found that the addition of Bi₂O₃ has an effect on relieving volume expansion during cycling, and consequently they showed specific capacity of ca. 400 mA h g^-1 after 30 cycles when the ratio of bismuth oxide/phosphorus is 3:1. It is profoundly investigated that the mechanism for the electrochemical improvement of the NIBs by using systematic analyses tools of electrochemical and instrumental analyses of XRD, SEM and TEM.