Vacuum pyrolysis of cellulose within the temperature range of 300–500°C provides a tar fraction containing mainly levoglucosan and glucose condensation products. It was found that pyrolysis proceeds at a much faster rate at the higher temperatures without detrimental effect on the yields. At 400°C the reaction was essentially complete within 3 min yielding a tar that contained 39% levoglucosan and, upon mild acid hydrolysis, gave 49% D-glucose. The yields could be further improved by washing or treatment of cellulosic substrates with acids. Cotton hydrocellulose provided up to 58% levoglucosan or 77% D-glucose. This is the highest yield determined by unequivocal methods. Commonly available cellulosic materials such as wood and newsprint give very poor yields of levoglucosan. However, the yields could be improved substantially by acid washing or prehydrolysis to the extent that pyrolysis of these substrates may become an attractive industrial process. The data in this report provide the technical basis for such a process and resolve the existing controversies on the reported yields.