Electronic structures of layered oxychalcogenides LaCuOCh (Ch-S, Se, Te) were studied using relativistic ab initio band calculations to understand their optical and electronic properties. Step-like structures terminated with one or two sharp peaks were observed in low-temperature (10 K) optical absorption spectra. Third optical nonlinearity measurements supported that the sharp peaks came from split excitonic levels. The ab initio calculations reproduced well these characteristic structures in the spectra and proved that the step-like optical absorption structures originated from two-dimensional nature of the electronic structures associated with the layered crystal structure of LaCuOCh. The split energies of the excitonic levels were quantitatively explained by spin-orbit interaction in the chalcogen ions. (c) 2004 Elsevier B.V. All rights reserved.