Multi-walled carbon nanotubes (MCNTs) were used as a support for Rh-based catalysts for high pressure (20 bar) CO hydrogenation. 3 wt% Rh/CNTs catalysts were loaded with 1 wt% and 2 wt% Mn promoter, respectively, in order to study the effect of metal-promoter interactions for ethanol synthesis. Both STEM and EXAFS results showed similar to 1 nmRh particles in promoted as well as the unpromoted catalysts, STEM and EELS results verified the enhanced metal-promoter interaction when the amount of Mn promoter increased from 1 wt% to 2 wt%. The enhancement in the degree of metal-promoter interaction leads to an increase in the ethanol selectivity. Moreover, due to the nature of CNTs (low Z number), the Mn-Rh interactions could be observed at atomic resolution during the STEM-EELS characterization, and the promoter phase is confirmed as Mn(II) oxide by}CANES and EELS. (C) 2014 Elsevier Inc. All rights reserved.