Silicon-based photovoltaic cells are currently the most dominant types applied to convert solar energy to electricity. In solar-grade silicon (SG-Si), the control of boron (B) and phosphorus (P) is very critical. Generally, these elements are difficult to remove into acceptable sub-ppm levels from lower grade Si. This study investigates slag treatment as a process for Si refining, focusing on the behaviour of P and B. The experiments were conducted by equilibrating Si-B-P alloys with 43 wt per cent SiO2 – 47 wt per cent CaO – 10 wt per cent Al2O3 slag under inert atmosphere at 1500°C. Different crucible materials were used (Al2O3, SiO2 and MgO), which determined the primary saturation phase for the system and modified the final slag composition accordingly. The samples were equilibrated and analysed with microanalysis techniques (EPMA (electron probe microanalysis) and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry)). New standards were prepared and applied in the LA-ICP-MS analyses. Experimental results show that silver is essentially fully dissolved in silicon, as well as most phosphorus with LP ( = wt per cent P in slag/wt per cent P in Si) between 0.1–0.3. The distribution coefficient of boron was measured to be between 1 and 2. The crucible material used had an influence on the phase compositions and slight influence on the distribution coefficients of boron and phosphorus. The experimental results provided new accurate data when considering applicability of slag treatment as a technique for Si refining and Si PV cell recycling.