This paper presents a comprehensive study on the carbonation of sodium metaborate (NaBO2) and the synthesis of high added value chemicals via NaBO2 and carbon dioxide (CO2). Carbon dioxide (CO2) is a greenhouse gas and NaBO2 is a by-product of sodium borohydride (NaBH4) hydrolysis reaction to produce H-2. Therefore their transformation into commercial chemicals is quite important in order to provide a mutual benefit to global warming issue and hydrogen economy. In the presented study, reaction parameters such as hydration factor, furnace type, calcination temperature, and environment are investigated at different levels and optimized. The effects of those key parameters on CO2 fixation yield are discussed. It is found that 400 degrees C is a key temperature for dehydration and reaction steps. Both dehydrated NaBO2 is obtained and maximum carbonation conversion is reached at 400 degrees C. Moreover, at relatively low temperatures (below 400 degrees C), a new reaction pathway is proposed and proved by thermodynamic calculations. Structural properties of NaBO2 are exhibited differences regard to thermal exposure and the conversion is strictly related to the structural properties.