DFT calculations of ground-state hydrazine and benzohydrazide derivatives were performed by using hybrid functional B3LYP and CAMB3LYP with 6–31G (d, p) as basis set. The electric dipole moment (μ), polarizability (α) and molecular first hyperpolarizability (β) were characterized in these compounds. The HOMO–LUMO energy gaps and the global chemical reactivity descriptors were computed by B3LYP and CAMB3LYP using 6–31G (d,p), while the excitation energies have determined by time dependent DFT (TDDFT). Besides, the stability and charge delocalization were studied by natural bond orbital analysis. Topological analyses such as atom in molecule (AIM), natural bonding orbital (NBO) and molecular electrostatic potential (MEP) have used to compute intermolecular interactions and in particular hydrogen bonds. The obtained first-order hyperpolarizabilities in the range of 1.5 × 10−30 to 30.2 × 10−30 esu revealed that the hydrazine and benzohydrazide derivatives have better NLO properties. The low-energy gap of 3.53 eV generates an intramolecular charge transfer, leading to the enhancement of the NLO activity in these compounds.