Unsupported bimetallic sulfide catalysts were obtained in situ using Mo(CO)(6) and Co octoate as precursors to investigate the promotional effect of Co on the MoS2 catalyst in the hydrocracking (HCK) of vacuum residue (VR). Transmission electron microscopy (TEM) and X-ray absorption fine structure spectroscopy were used to obtain structural properties of the catalysts. The bimetallic CoMoS2 catalyst exhibited high catalytic activity in the VR HCK with respect to the H-2 consumption rate and asphaltene conversion as compared with monometallic sulfides such as Co9S8 or MoS2 with the same catalyst loading of 0.113 mmol at 673 K and 9.5 MPa H-2. Higher hydrodesulfurization activity was also observed for the CoMoS2 catalyst. Moreover, extended X-ray absorption fine structure and TEM analysis identified the formation of a Co-Mo-S phase in monoslab particles of average particle size 6.7 nm and the maintenance of the morphology during five times of recycle tests. These results thus suggest that the unsupported CoMoS2 catalyst has a promotional effect on VR HCK. (C) 2019 Elsevier Inc. All rights reserved.