The use of mesoporous silica films for the production and study of positronium (Ps) atoms has become increasingly important in recent years, providing a robust source of free Ps in vacuum that may be used for a wide variety of experiments, including precision spectroscopy and the production of antihydrogen. The ability of mesoporous materials to cool and confine Ps has also been utilized to conduct measurements of Ps–Ps scattering and Ps2 molecule formation, and this approach offers the possibility of making a sufficiently dense and cold Ps ensemble to realize a Ps Bose–Einstein condensate. As a result there is great interest in studying the dynamics of Ps atoms inside such mesoporous structures, and how their morphology affects Ps cooling, diffusion and emission into vacuum. It is now well established that Ps atoms are initially created in the bulk of such materials and are subsequently ejected into the internal voids with energies of the order of 1 eV, whereupon they rapidly cool via hundreds of thousands of wall collisions. This process can lead to thermalisation to the ambient sample temperature, but will be arrested when the Ps deBroglie wavelength approaches the size of the confining mesopores. At this point diffusion through the pore network can only proceed via tunneling, at a much slower rate. An important question then becomes, how long does it take for the Ps atoms to cool and escape into vacuum? In a direct measurement of this process, conducted using laser-enhanced positronium time-of-flight spectroscopy, we show that cooling to the quantum confinement regime in a film with approximately 5 nm diameter pores is nearly complete within 5 ns, and that emission into vacuum takes ∼10 ns when the incident positron beam energy is 5 keV. The observed dependence of the Ps emission time on the positron implantation energy supports the idea that quantum confined Ps does not sample all of the available pore volume, but rather is limited to a subset of the mesoporous network.