Third harmonic generation experiments were performed on a type-I phase-matching La2CaB10O19 crystal cut at θ=49.4° and φ=0.0° with dimensions of 4.0 mm×4.0 mm×17.6 mm. A 1064 nm laser with a maximum average power of 35.2 W was employed as the fundamental light source, which has a pulse width of 10 picoseconds and a pulse repetition rate of 80 MHz. A type-I noncritical phase-matching LBO crystal was used to generate 532 nm lasers. By investigating a series of focusing lens combinations, a picosecond 355 nm laser of 5.3 W was obtained, which is the highest power of picosecond 355 nm laser based on a La2CaB10O19 crystal so far. The total conversion efficiency from 1064 to 355 nm was up to 15.1%.