Phosphorus poisoning and its effect on the diesel oxidation catalysts morphology was studied by transmission electron microscopy (TEM). The studied catalyst samples were PtPd or Pt supported on the alumina-based washcoat including additives. The laboratory-scale phosphorus exposures were carried out with two different phosphorus concentrations. The cross-sectional TEM samples were prepared from the fresh and phosphorus-treated catalysts. After phosphorus exposures, significant structural changes were observed compared to the fresh catalysts. The shape of the noble metal particles had changed from irregular to more spherical-shaped particles. In addition, phosphorus was detected throughout the catalyst TEM samples but the amount varied depending on the local composition of the support. Phosphorus accumulated mainly in the alumina-containing areas of the support and indications of dense and amorphous aluminium phosphates were found. Based on the results gained, cross-sectional TEM characterization is essential to observe these kinds of morphological changes in the catalysts caused e.g. by phosphorus exposures. In addition, cross-sectional TEM samples are needed to study the effect of local variation in the support composition on the phosphorus accumulation.