Boron speciation was investigated in soda-lime borosilicate glass containing zirconium. In such compositions, competition between charge compensators (here, sodium and calcium) can occur for the compensation of tetrahedral boron or octahedral zirconium units. 11B MAS NMR is particularly suitable for obtaining data on preferential compensation behavior that directly affects the boron coordination number. In addition to the classical proportions of tri- and tetrahedral boron, additional data can be obtained on the contributions involved in these two coordination numbers. An approach is described here based on simultaneous MAS spectrum analysis of borosilicate glass with variable Zr/Si and Ca/Na ratios at two magnetic field strengths (11.7 and 18.8 T), with constraints arising from MQMAS spectroscopy, detailed analysis of satellite transitions, and spin-echo experiments. New possibilities of 11B NMR were presented for improving the identification and quantification of the different contributions involved in tri- and tetrahedral boron coordination. Both NMR and Raman revealed a trend of decreased tetrahedral boron proportion with the increase of Ca/Na ratio or the Zr/Si ratio. This strongly suggests that zirconium compensation takes preference over boron compensation, and that zirconium and boron are both compensated mainly by sodium rather than calcium.