Control of phase separation of VO43- and rare earth precursors in reverse microemulsions afforded ∼35 nm YVO4 nanoparticles with functionalisable ∼7 ± 3 nm nanopores. Doping by Eu3+ allowed luminescent probing of interfacial crystallisation while xylenol orange absorption showed molecular encapsulation in particle cavities. This provides potential multifunctional systems combining UV-Vis-NIR luminescence and (photo)active molecules for optical sensing.