Chemical modification by SOCl2 of an entangled network of purified single-wall carbon nanotubes, also known as 'bucky paper', is reported to profoundly change the electrical and mechanical properties of this system. Four-probe measurements indicate a conductivity increase by up to a factor of 5 at room temperature and an even more pronounced increase at lower temperatures. This chemical modification also improves the mechanical properties of SWNT networks. Whereas the pristine sample shows an overall semiconducting character, the modified material behaves as a metal. The effect of SOCl2 is studied in terms of chemical doping of the nanotube network. We identified the microscopic origin of these changes using SEM, XPS, NEXAFS, EDX, and Raman spectroscopy measurements and ab initio calculations. We interpret the SOCl2-induced conductivity increase by p-type doping of the pristine material. This conclusion is reached by electronic structure calculations, which indicate a Fermi level shift into the valence band, and is consistent with the temperature dependence of the thermopower.