Mesoporous silica films and MFI-type pure silica zeolite films were investigated using slow positrons. Detection of the 3 gamma annihilation fraction was used as a quick test to estimate the emission of orthopositronium (o-Ps) into vacuum. Positronium time-of-flight (TOF) spectroscopy, combined with Monte-Carlo simulation of the detection system was used to determine the energy of o-Ps emitted from the films. Evidence for an efficient o-Ps emission was found in both themesoporous and silicalite-1. A 3 gamma fraction in the range of 31-36 % was found in the films with the highest o-Ps yield in each type of porous material, indicating that 40-50 % of the implanted positrons form positronium in the pore systems with very different pore sizes. Time-of-flight measurements showed that the energy of the orthopositronium emitted into vacuumis below 100 meV in the film with 2-3 nm pores at 3 keV positron energy, indicating an efficient slowing down but no complete thermalization in the porous films of 300-400 nm thickness. (C) 2008 Elsevier B.V. All rights reserved.