Positron annihilation lifetime measurements are performed for sol–gel-derived 70 mol% SiO2–30 mol% CaO bioactive glass. Strong positronium formation processes are shown to be an inherent feature for these kinds of materials. Observed orthopositronium (o-Ps) lifetimes show a three-modal distribution with lifetime values weighed at ∼2, ∼18, and ∼70 ns. The exposure of the investigated sol–gel-derived bioactive glasses to water vapor significantly modifies o-Ps lifetime distribution due to the penetration of water molecules into the nanopores, indicating high ratio of their interconnectivity. Classic Tao–Eldrup equation is used to relate the o-Ps lifetimes with the size of nanopores, whose distribution is verified by nitrogen adsorption porosimetry.