CO2 hydrogenation to CH3OH under relatively lower temperature has considered an important but still challenging task. Herein, nanoporous Co (NP-Co) and a series of modified NP-CoxM (M=Cr, V, Mo, Mn, Ce, W, x=nCo∶nM) were synthesized and evaluated for CO2 hydrogenation to CH3OH at 60-140 °C. Cr element as an additive seems to be favorable for the promotion of catalytic performance. N2 adsorption-desorption, SEM, TEM, XRD, XPS and CO2-TPD were employed for the characterization of NP-Co and NP-CoCrx. Results showed the addition of CrOx enhanced the strong interaction between CO2 and the catalytic active site. In addition, the large increase of surface hydroxyl promoted the activation of CO2 under relatively lower temperature, which was manifested as the significant reduction of apparent activation energy for NP-Co3Cr (59.08 kJ/mol) compared with NP-Co (89.12 kJ/mol). CH3OH as a major product exhibited time yield of 106.4 μmol/（gCat.·h） at 60 °C and selectivity was up to 92.8%, while no CH3OH generated with NP-Co catalyst under the same reaction conditions.