The interplay between the thermal helical inversion (THI) of the stiff-stilbene moiety and the rotation of the dimethylamino (DMA) group in 1 results in a dependence of the DMA NMR signals on the THI kinetics in (E)-1 but the rotation kinetics in (Z)-1, because the faster motion mode is responsible. Consequently, the photochemical switching from (E)-1 to (Z)-1 illustrates the phenomenon of "switchable motion detection" by the same set of NMR signals in a dual-motion molecular system.