A high intensity 464 nm excitable ZnWO4:Eu3+ red‐emitting phosphor for warm white lighting applications was prepared using a solid‐state reaction method by varying the dopant Eu3+ concentration. Crystalline purity and phase identification was confirmed and revealed using powder X‐ray diffraction and Rietveld refinement analysis. The surface morphology of Zn1‐xEuxWO4 (x = 0, 0.01, 0.02, 0.03, 0.04 and 0.05) was examined using scanning electron microscopy (SEM) techniques. From SEM analysis, the ZnWO4:Eu3+ phosphor prepared at 1–3% molar Eu3+ concentrations exhibited a small pebble‐like morphology with a smooth surface. On increasing the molar concentration of Eu3+ to >3%, the pebble stone morphology disappeared and a large, smooth irregular polygon‐shaped granular‐like morphology was obtained. Of the higher mol% Eu3+, the 4% Eu3+‐doped ZnWO4 showed the best photoluminescence properties with high intensity and sharp excitation at 395 and 464 nm, followed by red emission centred at 615 nm with excellent CIE coordinates (x = 0.58 and y = 0.41) in the core red region. Elemental composition and chemical state analysis were carried out for the 4% Eu3+‐doped ZnWO4 phosphor using X‐ray photoelectron spectroscopy and energy dispersive X‐ray spectroscopy studies. Based on all the above analyses, the Eu3+‐doped ZnWO4 phosphor was found to be a very efficient red‐emitting phosphor under near‐UV light as well as under visible light excitation and could be used for white LED and field emissive displays applications.