For the first time, it was found that dry-grinding the mixture containing technical grade PdO and multiwalled carbon nanotubes (MWCNTs) can generate a catalyst with ultrahigh electrocatalytic activity for ethanol oxidation reaction (EOR). The as-prepared catalysts were denoted as PdO/MWCNTs. For a comparison, the graphene and graphite supported PdO samples were also prepared using the same process, leading to the formation of PdO/graphene and PdO/graphite catalysts respectively. The structural details, the morphologies as well as the particle sizes of the prepared catalysts are mainly characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Although no novel diffraction peaks were observed in the XRD patterns of the resulting samples, the morphologies of the samples after the dry-grinding process have changed greatly as compared to the starting materials of PdO. The results also indicate that the PdO/MWCNTs catalysts show the smallest particle sizes among all the prepared catalysts. The catalytic activities of the prepared PdO/MWCNTs catalysts towards EOR are examined by electrochemical measurements, and the results obtained from cyclic voltammery (CV) test demonstrated that the PdO/MWCNTs catalyst delivers a forward peak current density for EOR of 5029 mA mg(-1) at a scan rate of 50 mV s(-1), which is about 2.1 times higher than the reported value (2361 mA mg(-1)) obtained on the (Pd/C) catalyst. After detailed analysis, it is thought that the easier hydrogen evolution process on the PdO/MWCNTs catalyst is regarded as the main reason for its excellent electrochemical performance as compared to other catalysts, i.e., PdO/graphene and PdO/graphite. Most interestingly, the as-prepared catalyst has electrocatalytic activity for both methanol oxidation reaction and formic acid oxidation, which were also explored approximately in this preliminary work. (C) 2014 Elsevier Ltd. All rights reserved.