Cereal straw is a biomaterial with great potential: about 144 million tons of biomass are grown annually in Europe. For any use of straw (fertilizer, biofuel, etc.), efficient chopping technology, i.e., the reliable and efficient operation of mobile or stationary choppers, is the key factor for further success. Since most of the straw is chopped at harvest time, the subject of the study is the wear of the combine’s chopping knives. Six blades of different materials and designs were tested under realistic conditions during wheat and rapeseed harvesting on 180 ha. The influence of hardness, composition, cutting edge angle, and position in the chopper on knife wear was analyzed. The study showed that the blades with the highest cutting edge hardness (568 ± 11 HV) and the lowest cutting edge angle (20.9°) had the lowest wear. The highest hardness of the induction hardened knives was due to the 0.42% carbon content of the steel. The study confirmed that wear was inversely proportional to the hardness of the cutting edge (the harder the cutting edge, the lower the wear) and directly proportional to the angle of the cutting edge (the higher the angle, the greater the wear). The SEM study showed that part of the tooth surface of the blades was covered by permanent deposits of the material to be shredded. This wear was not caused by the interaction between straw and blade but by microabrasive particles that contaminated the straw.