A dual-emission long persistent luminescence phosphor SrZrO₃: Yb³⁺ is synthesized through a conventional high-temperature solid-state reaction method. A combined experiment and first-principles methods are carried out to study the inner link between the electronic structures and spectroscopic characteristics of SrZrO₃: Yb³⁺ phosphor. The calculation shows that the incorporation of Yb³⁺ ions into SrZrO₃ lattice can be done through substituting Yb³⁺ ions for Sr site. It is found that vacancy defects of SrZrO₃: Yb³⁺ system easily produce around the doping positions. Especially, the oxygen vacancies, which are deduced as the intrinsic vacancy defect, are responsible for the persistent luminescence in SrZrO₃: Yb³⁺ phosphor. The persistent luminescence of SrZrO₃: Yb³⁺ consists of two parts: near-ultraviolet persistence originate from self-trapped excitons of host, and near-infrared one stems from ²F_5/2 → ²F_7/2 transitions of Yb³⁺. The photoluminescence and persistent performance are studied as function of the concentration of Yb³⁺ ions. The optimal concentration of Yb³⁺ ions for the photoluminescence emission and long persistent luminescence are both approximately 2.5%. The long persistent luminescence mechanism for SrZrO₃:Yb³⁺ is illuminated on the basis of photoluminescence and first-principle calculation results.