We experimentally and theoretically studied cellulose pyrolysis at high temperature and short residence time. We investigated the gas phase chemistry with dedicated experiments and feeding intermediates. Results have been also compared with equilibrium calculations, both single (gas) phase and allowing for solid C formation. Our aim was to understand the cellulose degradation mechanism and particularly the role of gas phase chemistry. We provided evidence of a simplified mechanism, where CO formation is a first, fast step that can be related to levoglucosan ring opening, while H-2 comes from a totally different route, based on hydrocarbon reforming reactions, which also provide further CO. In addition, butadiene was identified as a key intermediate in the decomposition sequence. The different paths and rates of CO formation and H2 formation explain why the ratio of CO to H-2 is not constant, particularly at short residence time. A two-stage process or longer contact time is required, if aiming at syngas production.