In this paper, we synthesise and determine the structures of a series of A-site vacancy-ordered double perovskites A 1-x {Ni + 2 [Bi(SCN) 6 ] 1-x 3 }, A = K + , NH + 4 , MeNH + 3 and C(NH 2 ) + 3 (Gua + ). We thus show that larger A-site cations can be incorporated into NCS-perovskites. We demonstrate that the identity of A-site cation plays a critical role in the structure of thiocyanate perovskites, and that new and unusual combinations of A-site order , M-site order and octahedral tilt patterns can be readily achieved in these materials. In particular, we show using a combination of X-ray and neutron diffraction and density functional theory (DFT) calculations that the A-site cation order and octahedral tilts are strongly coupled. Inspired by these structures, we use symmetry analysis and DFT calculations to suggest the combination of complex orders found in thiocyanate perovskites could be used to produce cooperative properties such as piezoelectricity.