The photoionization of neutral liquid helium droplets (mean particle number [N] = 10(2)-10(7)) was studied using synchrotron radiation at photon energies ranging from 15 to 30 eV. Mass spectra as well as total and mass selective ion yields were measured as a function of the photon energy for different droplet sizes, The experiments indicate that ionization occurs not only by a direct process at photon energies above the atomic ionization potential. but also at energies below the threshold by an autoionization process, The latter ionization mechanism proceeds via the electronically excited states of the neutral droplet, which show a strong neutral droplet size dependence. For large neutral droplets He-N([N] > 10(4)) retarding held measurements established that a predominant part of the total ion yield results from larger cluster ions He-k(+)(k > 10(3)). These measurements also show that a decay by fluorescence emission is much more probable than one by ionization following the photoexcitation process. In droplets with embedded SF6 molecules these are ionized indirectly by Penning ionization via excitons which leads to a large ion signal on the mass of the embedded species. No evidence for direct photoionization of the impurities was found.