Unfilled tetragonal tungsten bronze (TTB) structure Ba4LaTiNb9O30 doped by Eu3+ (BLTN: Eu(3+)x) with different x have been prepared, and their structural, photoluminescence, dielectric, and ferroelectric properties are carefully investigated in this work. Bright red emission, originating from D-5(0) -> F-7(1) and D-5(0) -> F-7(1) transitions of Eu3+ ions, has been observed by naked eyes at room temperature under near ultraviolet (NUV) light excitation. Optimized emission intensity is obtained when x = 1.00 for present unfilled TTB-type BLTN: Eu(3+)x samples. Furthermore, with increasing x, the dielectric and ferroelectric characteristics of the unfilled TTB-type BLTN: Eu(3+)x samples also display remarkable variation. When x >= 0.50 relaxor-like ferroelectric phase transitions are detected above room temperature, it is believed that unfilled TTB-type BLTN: Eu(3+)x = 1.00 involving bright photoluminescence and enhanced ferroelectric properties may act as a potentially multifunctional optical-electro material. (C) 2014 Elsevier Ltd. All rights reserved.