The lead-free Eu3+ doped (SrxBa1-x)0.98Eu0.02Nb2O6 (SBEN, 0.3 ≤ x ≤ 07) ceramics were fabricated by conventional solid-state reaction method. Eu3+ was chosen as a dopant with the goal of inducing strong red-emitting photoluminescence based on their electrical properties. Effects of Sr/Ba ratio on the crystal structure, dielectric, ferroelectric and photoluminescent properties of SBEN ceramics were investigated by changing x. Single tungsten bronze structure with P4bm space group was obtained for all ceramics. The ceramics grain morphology varied obviously from homogenous equiaxed shape to anisometric pillar-type shape with increasing x. According to the dielectric spectra, the obtained SBEN ceramics transited from normal ferroelectrics to relaxor ferroelectrics, accompanied by the gradual decrease of Tm with increasing Sr2+ amount in A-sites. Two strong emitting peaks corresponding to the orange magnetic dipole transitions (594 nm, 5D0→7F1) and red electric dipole transitions (618 nm, 5D0→7F2) were obtained for all SBEN ceramics. The red/orange-emitting ratio of Eu3+ related to the Sr/Ba ratio in the composition was studied in this work to discuss the ions occupying situation in different A-sites.