A new copper indium selenide, Ba3.5Cu7.55In1.15Se9, was synthesized by the KBr flux reaction at 800 °C. The compound crystallizes with orthorhombic Pnma, a = 46.1700(12) Å, b = 4.26710(10) Å, c = 19.8125(5) Å, and Z = 8. The structural framework mainly consists of four sites of cubane-type defective M4Se3 (M = Cu, Cu/In) units with disordered Cu+/In3+ ions present at the part corner of each unit. The single crystal emits intense photoluminescence at 657 nm with a relative quantum yield (RQY) 0.2 times that of rhodamine 6G powder. The compound belongs to a direct band gap at 1.91 eV, analyzed by Tauc's plot, and the energy is close to the PL position. The Hall effect measurement on a pressed pellet reveals an n-type conductivity with a carrier concentration of 3.358 × 1017 cm-3 and a mobility of 24.331 cm2 V-1 s-1. Furthermore, the compound produces a strong nonlinear third-harmonic generation (THG), with an χS(3) value of 1.3 × 105 pm2/V2 comparable to 1.6 × 105 pm2/V2 for AgGaSe2 measured at 800 nm.