Three 3-alkylpyridinium salts, pachychalines A (1), B (2) and C (3), were isolated from the Caribbean marine sponge Pachychalina sp. (order Haplosclerida). They are the first examples of 3-(aminoalkyl)pyridinium salts. Their chemical structures were elucidated by NMR spectroscopy and detailed ESI HRMS-MS analysis. The total synthesis of 1 allowed the confirmation of the unusual C-C connection between both pyridinium moieties. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).