octahedra are intrinsically non-polar. However, by combining octahedral tilts with other symmetry-breaking orders, such as A-site or M-site occupational order, we can generate polar structures: the so-called hybrid improper ferroelectrics. Furthermore, recent work has shown that the unusual framework distortions possible in molecular perovskites, such as unconventional tilts and columnar shifts, while non-polar, offer new routes to polarity. Creating materials capable of sustaining new ordering types and sustaining multiple simultaneous orders is therefore a powerful method for generating novel function. Gaining control over these orders, both individually and separately, remains one of the challenges of solid-state chemistry. One key guiding parameter is the tolerance factor τ = r A +r X r A is the radius of the A cation, r M is the radius of the M cation and r X is the radius of the X anion, which quantifies our intuition that the A-site cation has to fit well into the MX 3 cage. It indicates whether AMX 3 is likely to be a perovskite, rather than (τ > 1) 1D or 2D structure types (e.g. hexagonal 'perovskite') or (τ < 0.8) other, dense non-perovskite structure types (e.g. ilmenite). Although originally developed for atomic perovskites, the tolerance factor approach can rationalise the structures of a wide-range of molecular perovskites, including formates and alkylammonium metal halides, and its fundamental geometric insight has been generalised to other systems. τ is also linked to the size of the octahedral tilts, as smaller τ tends to require large tilts to retain a dense structure. However, creating new function requires controlling the relative sense of the tilts, i.e. whether each layer of octahedral tilts rotates in same sense as the next (a + in the Glazer notation ), or opposite sense (a -), not just their magnitude. This remains challenging to predict for new perovskites. τ can be readily tuned by creating solid solutions of cations (or cations and vacancies) on the A or M site, as the entropy of mixing stabilises these phases at the high synthesis temperatures used. Conversely, this means that cation-ordering is uncommon, particularly on the A-site. A-site order is most often stabilised by large size differences between A-site cations, especially the extremal size difference between a vacancy and a cation, and therefore typically produces layered order which minimises the local strain, e.g. (2 = vacancy, Ln = lanthanide). M-site order is stabilised by large charge differences, which favours rocksalt order (the 'double perovskite' structure) for electrostatic reasons. Simultaneous control of these A-site and M-site occupational orders to make so called 'double double' perovskites requires therefore specific chemical compositions, but can produce new function e.g. polarity in NaLaMnWO 6 . Rarer A-site occupational orders are typically stabilised by coupling the A-site order to octahedral tilt distortions of the MX 3 framework. Notably, CaFeTi 2 O 6 has the unusual a + a + c -tilt sequence which facilitates columnar A-site order and the a + a + a + tilt sequence found in CaCu 3 Ti 4 O 12 stabilises 3:1 Cu 3 Au-type Asite order. These challenges means the synthesis of double double perovskites often requires specialist conditions such as high pressure. Molecular perovskites are fertile ground for the exploration of multiple simultaneous orders because of their chemical diversity, low temperature syntheses, and the toolbox of crystal engineering (e.g. H-bonding). We focus in this paper on the family of perovskite-like materials derived from thiocyanate, A x {M[M (SCN) 6 ]}, of particular interest for their catalytic and optical function. These NCS-perovskites have complete Msite order, due to the difference between N-and S-termini of the ligand, and have large tilts due to the frontier molecular orbitals of the NCS -ligand. The robustness of these distortions means NCS-perovskites are an ideal platform for exploring complex orderings.