In the present study it is demonstrated that Mössbauer emission spectroscopy (MES) can generate information on the various Ni phases present in sulfided Ni containing catalysts when a small amount of 57Co is used as a probe for Ni.Application of MES to 57Co:Ni(4.5)Mo(8.0)/C and 57Co:Ni(5.6)/C revealed the formation of a so-called "Ni-Mo-S" phase in the former and a bulk sulfide in the latter catalyst. After addition of phosphorus a "Ni-(thio)phosphate" phase is found to be formed in both catalysts.The relation between the structure of these catalysts and their activity for thiophene HDS and quinoline HDN is discussed