Single crystal of hybrid framework of Piperazinium Perchlorate (PPCL) has been achieved by Slow Evaporation Solution Technique (SEST). The result of various growth parameters and different physico-chemical characterization of PPCL crystals were studied. The Single Crystal X-Ray Diffraction was used to identify the 3D molecular structure and unit cell parameters of the grown PPCL crystal. The optimized geometry, vibrational wavenumbers, HOMO-LUMO energy gap were computed by B3LYP level of theory with 6–31++G (d,p) basis set. The theoretical calculations performed by Density Functional Theory agree with the obtained experimental results. The reported FT-IR and FT-Raman spectral studies explore the modes of vibration of different functional groups present in the PPCL crystal. UV–visible NIR transmittance studies revealed that the grown crystal possesses high transmittance in the entire visible region. The third-order nonlinear optical properties were carried out by Z-scan technique using Q-switched Nd: YAG laser at 532 nm. © 2020 Elsevier B.V.