Purely organic chiral molecular assemblies in the solid state hold great potential for non‐linear optical applications. Herein, a newly synthesised molecular system is reported, namely, dicinnamalacetone, an otherwise planar molecule that crystallises in a disordered non‐centrosymmetric form with four different conformations having an overall predominance of a particular helicity. A combined experimental and theoretical approach, including single‐crystal X‐ray diffraction, Kurtz–Perry and ab initio methods, is employed to characterise the system and benchmark the performance of hybrid functionals for the prediction of non‐linear optical properties and electronic excitations. Comparison of experiment and theory points to a particular set of hybrid functionals that provides an optimal description of this molecular system.