Phase relations in the lime-rich portion of the system CaO-B₂O₃-SiO₂ have been studied by microscopy, infrared spectroscopy and X-ray powder diffraction of heated mixtures and quenched charges. Extensive solid solution of B₂O₃ in Ca₂SiO₄ occurs along the Ca₂SiO₄-Ca₃B₂O₆ boundary, which has been studied in detail. It contains a ternary compound, Ca₁₁B₂Si₄O₂₂, which is stable to liquidus temperatures, melting incongruently to Ca₂SiO₄ and liquid at 1420 °C. Ca₁₁B₂Si₄O₂₂forms a eutectic with Ca₃B₂O₆ at 1400 °C and, in the ternary system, with CaO and Ca₃B₂O₆ at 1390 °C.