The steric effect for the XeCl*(B, C) formations in the oriented Xe* (P-3(2), M-J = 2) + oriented CCl3F reaction has been observed as a function of the mutual configuration between the molecular orientation and the atomic orbital alignment in the collision frame. Molecular steric opacity functions have been determined as a function of the atomic orbital alignment (ML') in the collision frame. The XeCl*(B, C) channels show similar molecular steric opacity functions at M-L' = 0 but not at vertical bar M-L'vertical bar = 1. The large molecular alignment dependence (i.e., the reactivity of the Cl-3 end and the F end is comparable, but a very poor reactivity for the sideway) is recognized for the XeCl*(B, C) channels except for the XeCl*(C) channel at vertical bar M-L'vertical bar = 1, which shows an almost isotropic molecular orientation dependence. The M-L' selectivity is different between the XeCl*(B, C) channels. At the molecular axis direction, the XeCl*(B) channel has little M-L': selectivity whereas the XeCl*(C) channel is significantly favorable at M-L' = 0. On the other hand, vertical bar M-L'vertical bar = 1 is favorable at the sideway for the XeCl*(B, C) channels.