A series of Eu3+ doped intergrowth Bi4Ti3O12–SrBi4Ti4O15 (BIT–SBTi: xEu3+) (0.0 ⩽ x ⩽ 4) ceramics were prepared through a solid-state reaction method. Contrast with conventional ferroelectric (FE) research, here, we report the photoluminescence (PL) properties of BIT–SBTi: xEu3+ system for the first time. Bright red emission was observed at room temperature. It should be noted that the red emission of BIT–SBTi: xEu3+ can be excited by both blue light and near ultraviolet (NUV) radiation. Optimized emission intensity was obtained when x = 2 for BIT–SBTi: xEu3+. Moreover, the FE and dielectric properties of BIT–SBTi: xEu3+ were also investigated. BIT–SBTi: xEu3+ with x = 0.7 ceramic exhibits optimized FE and dielectric behavior. The multifunctional properties of BIT–SBTi: xEu3+ ceramics were confirmed in this work.