An excellent green persistent luminescence (PersL) phosphor Zn2SiO4: Mn2+, Yb3+ was synthesized through a new method via reacting Zn-based coordination polymer particles with SiO2 submicrospheres. The structure properties including the phase purity, structural parameters and crystal structure were investigated in details. Morphological analysis revealed that Zn2SiO4: Mn2+, Yb3+ retained the morphology of SiO2 submicrospheres with diameter ∼200 nm. The PersL of Zn2SiO4: Mn2+ displayed a remarkably enhanced afterglow duration by codoping with Yb3+, in which the duration time prolonged from 5 min to 114 min (∼23 times) as compared with that of Zn2SiO4 host or singly Mn2+ doped. The depths of the traps responsible for PersL were estimated to be in the range of 0.696–1.112 eV, and an additional trap that are deemed to play a role for the improvement was discussed. The prepared phosphors were successfully used for the latent fingerprint visualization and exhibited high accuracy of fingerprint recognition. These findings not only provids a new synthetic approach for PersL materials with designated morphology and dimensions, but also indicates the product may find applications in advanced latent fingerprint identification, information storage and anticounterfeiting technology.