The GeO-B2O3-Na2O (GBNB)，GeO2-Al2O3-Na2O(GANB), GeO2-Al2O3-BaO(GABB)and GeO2-Al2O3-Y2O3(GAYB) glasses doped with bismuth of 1mol% concentration were prepared by melting method and measurement of their DTA curves, absorption and emission spectra and fluorescence decay curves were carried out. It was found that the absorption edges of GBNB，GANB，GAYB，GABB were red-shifted. Since the absorption edges are ascribed to the charge transfer transition from Bi3+ 6s2 to Bi5+ 6s0，we conclude that the content of Bi5+ in GBNB, GANB, GAYB, and GABB glasses increased gradually. Near infrared super-broadband emission of GANB, GABB and GAYB samples were observed to be center-peaked at ～1220nm. The fluorescence intensity, FWHM and emission lifetime of GABB，GAYB，GANB were reduced gradually. The super-broadband emissions may be due to the formation and fluorescence of Bi5+. It could be deduced from the absorption and emission spectra that the introductions of BaO and Y2O3 into GeO2-Al2O3 glass were advantageous to the formation of Bi5+ in the glass. The mechanism of BaO and Y2O3 composition affecting the formation of Bi5+ in the GeO2-Al2O3 glass is discussed.