The central goal of crystal engineering is to develop precise control over material function via rational design of structure. A particularly successful realisation of this paradigm is the example of hybrid improper ferroelectricity in layered perovskite materials, where cation vacancies and cooperative octahedral tilts combine to break inversion symmetry. However, in the more chemically diverse and technologically relevant family of ABX3 perovskites, symmetry conspires to render hybrid coupling to polar distortions impossible. Molecular substitution on the A- and/or X-site significantly diversifies the range of distortions possible. In this study, we use group-theoretical analysis to uncover a profound enhancement of the number of improper ferroelectric coupling schemes available to molecular perovskites. Not only do our insights rationalise the emergence of polarisation in a number of previously-studied materials, but we identify the fundamental importance of molecular degrees of freedom at the A-site, which are much more straightforwardly controlled from a synthetic viewpoint than are lattice, charge and orbital degrees of freedom. We envisage that the crystal design principles we develop here will be enable targeted synthesis of a large family of new acentric functional materials.