The effect of electrical poling on the room temperature structural, dielectric and photoluminescence properties of small concentration (i.e. 0.5 mole%) of Ho+3 substituted sodium bismuth titanate ferroelectric material (Na0.5Bi0.495Ho0.005TiO3 abbreviated as NBT-0.5Ho) has been investigated. Its crystal structure was found to be the mixture of two phases of rhombohedral (R3c) and monoclinic (Cc) in which monoclinic (Cc) coexisted as major phase. Comparative study of X-ray diffraction (XRD) patterns of electrically poled and unpoled specimens of NBT-0.5Ho revealed that electric field irreversibly transformed crystal structural of dominant Cc (˜94.05% phase fraction) phase to R3c (˜70.6% phase fraction) as major phase. Dielectric value and its dispersion with frequency were significantly decreased in poled specimen which is ascribed to electric field driven structural change. Two photoluminescence (PL) emissions at 655nm and 756nm were obtained in NBT-0.5Ho. PL intensity was considerably tuned in effect of electrical poling in term of quenching. Obtain quenching is correlated with induced structural ordering towards higher symmetry phase (R3c) in effect of electric poling which is confirmed from XRD analysis. Obtained additional functionality of photoluminescence in the NBT-0.5Ho ferroelectric material and its tuning in effect of electric field opens the possibility in the material for optoelectronic devices applications. © Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence.