Single crystals of undoped (pure) and barium nitrate (Ba (NO3)2)-doped L-Valinium Picrate (LVP) were grown from aqueous solution by slow evaporation technique. Morphological changes have been observed when Ba (NO3)2) is doped into LVP crystals. The dopant concentration in the crystals was measured by ICP technique. Slight changes in the unit cell parameter of LVP after doping with Ba (NO3)2) have been detected. The powder X-ray diffraction of the grown crystals has been recorded and the various planes of reflection identified shows shift in the peak positions. FTIR and UV spectra reveal the functional group identification and optical property of the grown crystals. The relative second harmonic generation (SHG) efficiency measurements revealed that both 5 and 10 mol % of Ba (NO3)2) in LVP enhanced the SHG efficiency by 92.85 and 160.59 times that of KDP respectively. However, at higher concentration, SHG efficiency is not increased but rather decreased from it undoped condition. Microhardness studies show that hardness number (Hv) increased with increase in load for all the grown crystals of this work.