In this study we have investigated how the identity of the A + cation determines the coupled A-site occupational order and octahedral tilt distortions of and Gua + , vacancy-ordered perovskites. We have shown that organic cations can be hosted as A-site cations in NCS-perovskites, and that the synthesis of large single crystals of these materials can be achieved via facile solution methods. NCSperovskites have robust M-site order and nearly fixed magnitude conventional octahedral tilts: in this work we have shown that A-site occupational order can also be readily achieved in NCSperovskites. We demonstrate that, by controlling these three orders at once, we can produce new and unprecedentedly complex perovskite structures, notably the non-Brillouin zone corner tilts and block A-site order found in (MeNH 3 )Ni[Bi(SCN) 6 ]. We have devised a simple counting method for predicting the coupling between octahedral tilts and A-site occupational order, supported by DFT calculations. Finally, we have shown how complex conventional tilts can produce new routes to non-centrosymmetric materials. These results suggest that exploration of NCS-perovskites and complex tilts more generally may uncover further functional behaviour, including ferroelectricity, and anomalous mechanical properties such as negative thermal expansion or negative linear compressibility.