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The structures of glasses in the lithium–bismuth orthoborate composition range deviate significantly from the short‐range order structure of the two crystalline end‐members. Although binary Li3BO3 and BiBO3 are solely of comprised trigonal orthoborate anions, all glasses formed by their combination contain four‐coordinated borate tetrahedra. We analyze the structure of (75−1.5x)Li2O–xBi2O3–(25+0.5x)B2O3 glasses in increments of x = 5, with 11B magic‐angle spinning nuclear magnetic resonance (NMR), infrared (IR), and Raman spectroscopy. For the full series, the oxygen‐to‐boron ratio remains constant at O/B = 3:1. NMR quantifies an increase in the fraction of tetrahedral boron with increasing bismuth oxide content. Evolution of the mid‐IR profile suggests multiple types of tetrahedral boron sites. Raman spectroscopy reveals that Bi2O3 tends to cluster within the lithium borate matrix when initially introduced and that this behavior transforms into a bismuthate network with increasing bismuth oxide content. In all cases, mixed Bi–O–B linkages are observed. The dual role of bismuth as network modifier and network former is likewise observed in the far IR. The glass transition temperature continuously increases with bismuth oxide content; however, the glass stability displays a maximum in the multicomponent glass of x = 40. [ABSTRACT FROM AUTHOR]