Exciting the CH-stretching mode of CHD(3) (where D is deuterium) is known to promote the C-H bond's reactivity toward chlorine (Cl) atom. Conventional wisdom ascribes the vibrational-rate enhancement to a widening of the cone of acceptance (i.e., the collective Cl approach trajectories that lead to reaction). A previous study of this reaction indicated an intriguing alignment effect by infrared laser-excited reagents, which on intuitive grounds is not fully compatible with the above interpretation. We report here an in-depth experimental study of reagent alignment effects in this reaction. Pronounced impacts are evident not only in total reactivity but also in product state and angular distributions. By contrasting the data with previously reported stereodynamics in reactions of unpolarized, excited CHD(3) with fluorine (F) and O((3)P), we elucidate the decisive role of long-range anisotropic interactions in steric control of this chemical reaction.