Synthesis, crystal structure and optical properties of two-dimensional layered inorganic-organic hybrid NH3(CH2)(12)NH3PbI4 are presented. Intercalation strategy has also been used to fabricate single crystal and thin films of the same. As thin film, they are well oriented and stacked along the [10 0] direction with strong room-temperature excitonic absorption and emission characteristics. Exciton features were correlated with the relative inorganic network crumpling and conformation of alkylammonium chains. The structural features are compared with those of similar hybrid, (H(CH2)(12)NH3)(2)PbI4. (C) 2010 Elsevier B.V. All rights reserved.