The surface‐enhanced local crystal structure of a series of ZnZrO3:Eu3+(1 to 5 mol.%) (ZZE) orange–red nanophosphors synthesized using a sol‐gel combustion process is investigated. X‐ray diffraction (XRD) with the Rietveld refinement analysis reveals a monoclinic ZnZrO3:Eu3+ structure with a space group 14. Field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM) analyses reveal the honeycomb alignment of nanoparticles in structure formation. The UV–vis‐diffuse reflectance spectroscopy (UV–vis‐DRS) analysis reveals strong absorption in the UV region, with an increase in the energy bandgap upon the addition of Eu3+ ions (1 to 5 mol.%). The optimized ZnZrO3:Eu3+(2 mol.%) nanophosphor exhibits high‐intensity orange‐red emission at 615 nm, as revealed by photoluminescence (PL) spectroscopy. Cyclic voltammetry (CV) analysis confirms the surface‐modified ZnZrO3:Eu3+ (2 mol.%) nanophosphor and hence reveals its electrochemical stability and selectivity to form stable suspensions with liquids or solids. ZnZrO3:Eu3+ (1 to 5 mol.%) exhibits fluorophore (Eu3+) embedded, surface‐enhanced Raman scattering, which opens new bioimaging applications. Further, the optimized ZnZrO3:Eu3+ (2 mol.%) nanophosphor investigated for the identification of latent fingerprint patterns (LFP) under visible light indicates its potential as a strong LFP‐revealing material in forensics without alternate light sources or chemical reagents.