We report herein a new rotation-inversion dual-motion molecular switch (1), in which a 3,3-dimethylazetidinyl (DMAZ) group is the rotator and a stiff-stilbene is the helical stator. There are two sets of nuclear magnetic resonance (NMR) signals in the DMAZ group, the H-shaped AZ protons and the planar C 2symmetrical Me protons, for probing the kinetics of the DMAZ rotation and the stiff-stilbene inversion. While the two motion modes are highly correlated in (E)-1, they are decoupled in (Z)-1. The rotation-inversion correlated motion in (E)-1 is governed by the faster inversion mode, whereas the inversion is much slower than the rotation in (Z)-1. Consequently, photochemical isomerization between (E)-1 and (Z)-1 switches not only the relative rate of the rotation versus inversion motion but also the on-off behavior of the rotation-inversion correlated motion. This work shows the cooperation of two sets of proton signals in elucidating the correlated motion in a dual-motion molecular system.