In this work, the performance of Ca 5 (BO 3 ) 3 F (CBF) single crystals was investigated for the third harmonic generation at 355 nm. A high energy conversion efficiency of 16.9% at 355 nm was reached using a two-conversion-stage setup. First, using a high peak power, passively Q-switched Nd 3+ :YAG/Cr 4+ :YAG microlaser based gain aperture in micro-MOPA, the second harmonic at 532 nm was achieved with lithium triborate (LBO) crystal, reaching 1.35 MW peak power. On a second step, laser pulses at 355 nm were generated using a 5 mm-long CBF crystal growth by TSSG method with energy, pulse duration and peak power of 479 µJ, 568 ps and 0.843 MW, respectively. These results are currently the highest reported for CBF material.