This account provides a summary of our research on poly (arylene-ethynylene)s (PAEs) containing dithia[3.3]metaphane such as dithia[3.3]metacyclophane and dithia[3.3](2,6)pyridinophane. Synthetic procedures, characterizations, optical properties, and their potential applications in a recyclable catalyst and metal sensor will be presented. To cite this article: Y Morisaki et al., C R. Chimie 12 (2009). (c) 2008 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.