Three new chiral phthalimides have been synthesized and characterized. Phthalimides (1–3) possess an acentric structure as revealed by structural investigation. Compounds 1 and 2 crystallize in an orthorhombic system with the space group P2₁2₁2₁, however the monoclinic system with the chiral space group P2₁ is observed for 3. The presence of C–H⋯O hydrogen bonds in 1–3 facilitates the construction of several supramolecular structures. Helical structural motifs are also observed. The maximum value of hyperpolarizability (β), 159.9446 × 10⁻³⁰ esu calculated for compound 3 is several times greater than that of urea. On the other hand 1 and 2 have hyperpolarizabilities of 10.8063 × 10⁻³⁰ and 121.9519 × 10⁻³⁰ esu, respectively. The polycrystalline samples of 1–3 were assessed for a second-harmonic generation response, which was found to be 8.8, 10.2 and 9.7 mV respectively. Further, compounds 1–3 showed d₃₃ values of 0.93, 1.97 and 1.88 pC N⁻¹ respectively. The present investigation demonstrates chiral phthalimides as effective contenders for nonlinear optical and piezoelectric properties.