Drawbacks, such as low laser damage threshold (LDT), of existing IR nonlinear optical (NLO) materials necessitate the exploration of new candidates. Promising candidates should have been found in the Ba–In–Q (Q = S, Se) system close to the well-known IR NLO (Ba, Sr)–(Ga, Al)–Q system, but all known Ba–In–Q phases are centrosymmetric (CS), precluding them from being NLO-active. Two new chalcogenides, Ba13Zn7In12S38 (1) and Ba12Zn8In12Se38 (2), were obtained by the introduction of d10 Zn2+ in the Ba–In–Q (Q = S, Se) system, where mixing Zn2+ in In3+ sites resulted in non-centrosymmetric transformation. Their structures comprised rare impeller-like chalcogenide units containing four-membered tetrahedral cluster or T2-supertetrahedra blades. Remarkably, strong phase-matchable second harmonic generation efficiency (0.6 × AGS), high LDT (24 × AGS), wide IR transparency region, and congruent melting characteristic make 1 be a good candidate for high power IR-NLO applications. The current work provided an avenue to design IR NLO materials in NLO-active motifs containing CS chalcogenide systems by the incorporation of d10 metals.