The introduction of co‐dopants is one of the effective ways to improve the luminescence properties of the persistent luminescence nanoparticles (PLNPs). Herein, Cr3+, Ca2+ co‐doped and Cr3+, Ca2+, Pr3+ tri‐doped β‐Ga2O3 PLNPs with enhanced persistent luminescence were developed via the hydrothermal synthesis and subsequent calcinations, which improved the persistent luminescence of the β‐Ga2O3 PLNPs. The results showed that the prepared PLNPs had a long afterglow time of more than 8 days with a signal‐to‐noise ratio (SNR) of 272 and the Quantum yield (QY) up to 74.8 %, which was renewable by LED lamps and stored information under a high‐temperature environment. The synthesized β‐Ga2O3:Cr3+, Ca2+, Pr3+ PLNPs with long afterglow time showed great potentials in optical storage. [ABSTRACT FROM AUTHOR]