Cubic cadmium(II) cyanide shows the most pronounced isotropic NTE effect known, with behaviour more than twice as extreme as that of better known materials such as ZrW2O8. This study aims to carry out an exploratory variable-T local structure study of 112Cd(CN)2 in the low temperature regime (10–300 K) with a number of important objectives: (i) to establish the extent to which ice-like rules govern the local Cd coordination environment (e.g. preference for CdC2N2); (ii) to determine the extent to which coordination environment is coupled to Cd off-centering; (iii) to identify the nature of collective NTE displacement modes populated on increasing temperature across the 10–300 K temperature regime; (iv) to determine the true Cd–C and Cd–N bond lengths for benchmarking our parallel DFT studies; (v) to identify any changes in local structure across the 150 K phase transition