A hyperthermal pulsed nozzle was developed to study the structure, energetics and dynamics of phthalocyanine-Ar, (n = 1, 2). The analysis of vibronic features revealed that the Ar atoms bind over the center of the phthalocyanine ring in both complexes. Despite little changes in energetics, the Ar complexation resulted in a significantly lower threshold energy for intramolecular vibrational redistribution in the 1:1 complex (similar to 474.2 cm(-1)) than in bare phthalocyanine (similar to 720 cm(-1)). Vibrational predissociation also starts at a somewhat higher energy (similar to 676.4 cm(-1)). The upper limits of intermolecular dissociation energy in the ground and excited states were 661.3 cm(-1) and 676.4 cm(-1), respectively.