Single crystals of N‐carbamothioylacetamide (NCTA) were grown by slow evaporation technique at constant temperature. The structure is elucidated by single crystal XRD analysis. The studies reveal that the molecule is associated with accommodating weak C–O···H, N–H···O, N–H···S, C–H···N, C···C and H···H stacking interactions which are responsible for the formation and strengthening of supramolecular assembly. Inter‐ and intramolecular hydrogen bonding interactions exhibit supramolecular architecture in the crystal packing. Two different types of architecture, i.e., a column like packing, and cluster network type of infrastructure are observed. Hirshfeld surfaces and Fingerprint plots were used to locate and analyze the percentage of hydrogen bonding interactions. The various functional groups present in the molecule are confirmed by FT‐IR analysis. Density functional theory computations of the vibrational spectrum, molecular geometry, HOMO‐LUMO energy gaps, NBO and hyperpolarizability (β) were successfully evaluated. Facts concerning with the size, shape, charge density distribution and site of chemical reactivity of the molecule have been obtained by mapping electron density with electrostatic potential (ESP).