Novel P-containing bulk Bi x Ga 5 Ge 20 P 10-x Se 45 Te 20 glasses have been successfully fabricated and studied with optical spectroscopy and differential scanning calorimetry. Non-isothermal and isothermal crystallization kinetics are investigated, and anti-Arrhenius behavior is observed for the crystallization of some phases in x = 1 glass. The thermal stability of the glass is shown to decrease with an increase in Bi concentration, whereas as the concentration of P increases, the glass stability increases and the glass does not crystallize during regular DSC heating scans. It is found that substitution of P with Bi in glass composition leads to a decrease in the optical gap and increase in its density.