A new noncentrosymmetric (NCS) and polar material containing two lone-pair cations, Bi3+ and I5+, and exhibiting an Aurivillius-type (Bi2O2)(2+) layer has been synthesized and structurally characterized. The material, BiO(IO3), exhibits strong second-harmonic generation (SHG), similar to 12.5 x KDP (or similar to 500 x alpha-SiO2), using 1064 nm radiation, and is found in the NCS polar orthorhombic space group Pca2(1) (No. 29). The structure consists of (Bi2O2)(2+) cationic layers that are connected to (IO3)(-) anions. The macroscopic polarity, observed along the c-axis direction, may be attributed to the alignment of the IO3 polyhedra. In addition to the crystal structure and SHG measurements, polarization and piezoelectric measurements were performed, as well as electronic structure analysis.