Novel [LPdCl]3 trimers (L = chiral secondary benzylamine) were synthesized via direct cyclopalladation. The structures of trimeric palladacycles were confirmed by means of X-ray analysis. The secondary interactions stabilizing trimeric molecules were investigated. An equilibrium between dimeric and trimeric palladacycle species was found in solution by means of dynamic NMR- spectroscopy and ESI mass spectrometry study.