Double perovskites with the general formula Bi2BB'O6 have attracted the attention since they can present multiferroic behaviour for some B-B' selected cations. More specifically, Bi2FeCrO6 and Bi2FeMnO6 have been studied both experimental and theoretically. The main divergence between the computational expected properties and the experimentally observed ones arises from the lack of cation ordering at the B position of the perovskite structure. We have recently synthesized some Bi2BB'O6 materials in bulk form under high pressure conditions (6 GPa). Preliminary structural refinements from laboratory XRD data show that these phases present evidences of cationic ordering at the B site, showing superstructure peaks and therefore indicating its potential as multiferroic materials. In this experiment, we aim to: i) investigate the crystal structure and its evolution with temperature, focusing specially in the cationic ordering and ii) determine its magnetic structure.