The main objective of this work is to prepare extruded niobium oxynitrides with macropores generation from niobium oxides varying: (i) the pore size distribution, burning polymeric molecules mixed with the precursor oxide before peptization; (ii) the final temperature of nitridation; (iii) the nitridation heating rate. The samples were characterized at different preparation stages. The specific pore volume increased up to five times without any loss of the total specific area. Some of these materials were employed in the cyclohexane dehydrogenation reaction. It was observed that they are active but they are less stable than molybdenum and tungsten oxynitrides when exposed to air. This behavior may be due to a faster superficial oxidation process. (C)2000 Elsevier Science B.V. All rights reserved.