This work investigates the role of a B₂O₃ addition (up to 21 mole %) into a lithium niobium silicate glass matrix, focusing on the orientational dependency of second harmonic generation (SHG), induced after femtosecond laser irradiation. We detected the sharp emission of light at 515 nm, characteristic of SHG, in both static and scanning configurations, using pulse energy, repetition rate, and laser polarization as varying parameters. Among the results to highlight, the SHG signature appears within a few seconds in highly doped B₂O₃ glass, i.e., one order of magnitude smaller than in B₂O₃-free glass. Additionally, we found that the orientability of the polar axis of LiNbO₃ nanocrystals by writing laser polarization can be obtained in glasses when SiO₂ is substituted with B₂O₃. These preliminary results open the door to the fabrication of crystal / glass based photonic devices with lower laser power deposited and much faster crystallization kinetics.