Electron energy-loss spectroscopy (EELS) is used to study the B distribution in a p-i-n layered solar cell structure. The boron concentration in the p-doped Si layer is expected to be ∼1021 cm−3 and should not exceed 1017 cm−3 in the neighbouring intrinsic layer. We show that B concentrations as low as 3×l020 cm−3 (0.6 at. %) can be measured using EELS. Our measurements are in close agreement with real space ab-initio multiple scattering calculations and secondary ion mass spectrometry measurements.