Reaction order in Bi-doped oxide glasses depends on the optical basicity of the glass host. Red and NIR photoluminescence (PL) bands result from Bi2+ and Bin clusters, respectively. Very similar centers are present in Bi-and Pb-doped oxide and chalcogenide glasses. Bi-implanted and Bi melt-doped chalcogenide glasses display new PL bands, indicating that new Bi centers are formed. Bi-related PL bands have been observed in glasses with very similar compositions to those in which carrier-type reversal has been observed, indicating that these phenomena are related to the same Bi centers, which we suggest are interstitial Bi2+ and Bi clusters.