We have studied B re-distribution in Si after excimer laser annealing (ELA) with multiple laser pulses. B was implanted using both B and BF2 ions with energies from 1 to 20 keV and doses of 1 × 1014 and 1 × 1015 cm−2. ELA with the number of pulses from 1 to 100 was performed in vacuum with the sample kept at room temperature and 450 °C. Independently of the implantation parameters and the ELA conditions used, a peak in the B concentration is observed near the maximum melting depth after 10 pulses of ELA. A detailed study has revealed that B accumulates at the maximum melt depth gradually with the number of ELA pulses. An increase in the carrier concentration at the maximum melt depth is observed after ELA with 100 pulses. No structural defects have been detected by transmission electron microscopy in the region of the B accumulation.