We report here on the observation of the Zr center dot center dot center dot F-CH3 van der Waals complexes in a laser ablation -supersonic expansion source. The complexes are studied using a combination of laser spectroscopy and time-of-flight mass spectrometric detection. We show that the (1: 1) Zr center dot center dot center dot F-CH3 complex is stable in the ground electronic state. By a ground state photodepletion method, we have characterized one of the transitions in the 600-700 nm region as correlating asymptotically with the z(3)F(2)(0)<- a(3)F(2) atomic transition from the ground state of free Zr atom. The corresponding excited state of the Zr center dot center dot center dot F-CH3 complex is reactive with activation of the C-F bond. (C) 2010 Elsevier B. V. All rights reserved.