Molecular orientation techniques are being used in the study of fundamental chemical processes to highlight structural and dynamical properties that are hidden by random rotational motion. More recently, successful orientation has been achieved for asymmetric tops and chiral molecules that are much more complex than hitherto. In this work, we report and discuss the optical fragment recoil velocity v, transition dipole moment μ, and permanent dipole moment The correlation between d. Slice ion images of Br*(2P1/2) and 2 bromobutane  photo fragments were acquired by (2 + 1) resonance-enhanced multiphoton ionization at 234.0 and 254.1 nm, respectively. Detailed analysis of sliced ion images acquired at a 45° laser polarization tilt angle provides information on the correlation of three vectors bounded by two polar angles α and χ and an azimuthal angle φμd in the recoil frame . The sliced ion image at 254.1 nm of the Br fragment individually eliminated from the enantiomer yielded an asymmetry factor close to zero; thus, the photofragmentation angular distributions showed no significant differences. The elimination of the Br* fragment at 234.0 nm is mainly associated with parallel transitions, yielding a large anisotropy parameter of 1.85 and thus can be considered as a singlet excitation. The resulting recoil frame angles α and χ were optimized to be 163°±8° and 164°±1°, respectively, while φμd was close to 0° for the best fit. Since for the molecules of the present invention the three vectors have only a slight spatial alignment, the light fragment angular distributions of the two enantiomers show no significant difference. Theoretical and computational simulations provide us with the basis to show that orientation enantiomers can be distinguished instantaneously even during photodissociation induced by non-circularly polarized light, as long as the three vectors encountered above have a specific three-dimensional arrangement. The fact that Br fragment elimination involves multipotential dissociation introduces uncertainties in the theoretical estimation of the vector orientation. Thus, this work represents a preliminary but important step on the road to dynamic chiral discrimination, which is best performed in molecules whose vectors are away from the degenerate mutual angular orientation.