In this work we report a straightforward method for the synthesis of a new class of small organic fluorophores bearing both [2.2]paracyclophane and naphthalene subunits using an intramolecular dehydrogenative Diels–Alder reaction as a key step. These compounds are characterized by a compact three-dimensional structure as well as through-space conjugated push–pull systems, and possess interesting spectroscopic characteristics that may be useful for the development of innovative chemical probes and optical sensors.