The chemical dynamics to form the D5-diphenyl molecule, C6H5C6D5, via the neutral-neutral reaction of phenyl radicals (C6H5) with D6-benzene (C6D6), was investigated in a crossed molecular beams experiment at a collision energy of 185 kJ mol(-1). The laboratory angular distribution and time-of-flight spectra of the C6H5C6D5 product were recorded at mass to charge mz of 159. Forward-convolution fitting of our data reveals that the reaction dynamics are governed by an initial addition of the phenyl radical to the pi electron density of the D6-benzene molecule yielding a short-lived C6H5C6D6 collision complex. The latter undergoes atomic deuterium elimination via a tight exit transition state located about 30 kJ mol(-1) above the separated reactants; the overall reaction to form D5-diphenyl from phenyl and D6-benzene was found to be weakly exoergic. The explicit identification of the D5-biphenyl molecules suggests that in high temperature combustion flames, a diphenyl molecule can be formed via a single collision event between a phenyl radical and a benzene molecule.