Designing second-order nonlinear-optical (NLO) materials with new structures is an attractive topic. Here, a novel type of sulfide borate, Eu2B5O9S, and one of its derivatives combining S2-, I-, and borate anions in one structure (three in one), viz., Eu-4.5(B5O9)(2)SI, are designed and synthesized with a high-temperature solid-state method. They crystallize in the noncentrosymmetric space group Pnn2. As the first sulfide borate being NLO-active, Eu-4.5(B5O9)(2)SI demonstrates good NLO behavior, namely, a moderate powder NLO response of ca. 0.5 times and a high laser-induced damage threshold (LIDT) of ca. 15 times those of AgGaS2, and is phase-matchable. The design strategy and experimental results are verified and explained by density functional theory calculations.