In this work, optical properties of a variety of boron host glasses with copper in relation to the lithium content from 0 to 25 % are studied. It is shown that with the increase of the lithium concentration the absorption band of Cu2+ increases. This fact is associated with the interaction of lithium ions in the melt with atmospheric oxygen. It is shown that the photoluminescence band shifts by more than 20 nm upon excitation at 320 nm with increasing lithium concentration. This is can be explained by the high splitting of the levels of Сu(I) under the action of lithium ions, and also with the formation of Cu+ -Cu+ dimers in the glass structure.