Photoluminescence properties of red-emitting Pr³⁺-doped Bi₂ZnOB₂O₆ microcrystalline powder and PMMA-based composite materials were reported. Bi₂ZnOB₂O₆:Pr³⁺ powders were synthesized by means of the modified Pechini method. The morphology and crystallographic structure of Bi₂ZnOB₂O₆:Pr³⁺ microcrystals were investigated by XRD and HRTEM. The PMMA-based composite materials were prepared by embedding of Bi₂ZnOB₂O₆:Pr³⁺ powder in the PMMA matrix. The vibrational properties of the powder and composite systems were investigated by μ-Raman spectroscopy. Emission spectra of the samples were measured under blue (451.6 nm) and UV (320 nm) excitation. Both, the powder and composite samples show enhancement of red emission (¹D₂ → ³H₄) and quenching of greenish-blue luminescence from ³P₀ level of Pr³⁺ ions after excitation in UV and VIS caused by the ³P₀ ∼ ¹D₂ non-radiative relaxation of Pr³⁺ ion by low-lying charge transfer state and non-radiative de-excitation through Pr³⁺–Bi³⁺ energy transfer. The response of the powder and composite samples to pulsed excitation at 451.6 nm was measured by monitoring emission from the ¹D₂ level (595 nm/³P₀ → ³H₆ transition). The determined lifetimes τ₁ and τ₂ of the red emission at 595 nm (¹D₂ → ³H₄ transition) of the composite are significantly longer in comparison to powder samples. Moreover, because of the good nonlinear optical properties of the Bi₂ZnOB₂O₆ crystals and effective luminescence of the Pr³⁺-doped Bi₂ZnOB₂O₆ powders and composites, they can be very useful as bi-functional materials in the new generation of optoelectronic devices.