A combination of liquid He droplet experiments and multi-reference electronic structure calculations is used to probe the potential energy surface for the reaction between the propargyl radical and O-2. Infrared laser spectroscopy is used to probe the outcome of the low temperature, liquid Hemediated reaction; Bands in the spectrum are assigned to the acetylenic CH stretch (nu(1)), the symmetric CH2 stretch (nu(1)), and the antisymmetric CH2 stretch (nu(13)) of the trans-acetylenic propargyl peroxy radical ((OO)-O-center dot-CH2-C CH). The observed band origins are in excellent agreement with previously reported anharmonic frequency computations for this species [Jochnowitz, E. B.; Zhang, X.; Nimlos, M. R.; Flowers, B. A.; Stanton, J. F.; Ellison, G. B. J. Phys. Chem. A 2010, 114, 1498]. The Stark spectrum of the ut band provides further evidence that the reaction leads only to the trans-acetylenic species. There are no other bands in the CH2 stretching region that can be attributed to any of the other three propargyl peroxy isomers/conformers that are predicted to be minimum energy structures (gauche-acetylenic, cis-allenic, and trans-allenic). There is also no evidence for the kinetic stabilization of a van der Waals complex between propargyl and O-2. A combination of multireference and coupled-cluster electronic structure calculations is used to probe the potential energy surface in the neighborhood of the transition state connecting reactants with the acetylenic adduct. The multireference based evaluation of the doublet-quartet splitting added to the coupled-cluster calculated quartet state energies yields what are likely the most accurate predictions for the doublet potential curve. This calculation suggests that there is no saddle point for the addition process, in agreement with the experimental observations. Other calculations suggest the possible presence of a small submerged barrier.