The synthesis and brakelike performance of a new molecular system (1) consisting of a pentiptycene rotor and a 2‐methyleneindanone brake are reported. The rotation kinetics of the rotor was probed by both variable‐temperature 1H and 13C NMR spectroscopy and DFT calculations, and the switching between the brake‐on and brake‐off states was conducted by a combination of photochemical and electrochemical isomerization. Because of the greater steric hindrance between the rotor and the brake units in the Z form ((Z)‐1) than in the E form ((E)‐1), rotation of the rotor is slowed down 500‐fold at room temperature (298 K) on going from (E)‐1 to (Z)‐1, corresponding to the brake‐off and brake‐on states, respectively. The (E)‐1→(Z)‐1 photoisomerization in acetonitrile is efficient and reaches an (E)‐1/(Z)‐1 ratio of 11:89 in the photostationary state upon excitation at 290 nm, attributable to a much larger isomerization quantum efficiency for (E)‐1 versus (Z)‐1. An efficient (Z)‐1→(E)‐1 isomerization (96 %) was also achieved by electrochemical treatment through the radical anionic intermediates. Consequently, the reversibility of the E–Z switching of 1 is as high as 85 %. The repeated E–Z switching of 1 with alternating photochemical and electrochemical treatments is also demonstrated.