Although Kaibel distillation columns are superior to conventional distillation sequences owing to smaller equipment investment and operation cost, they display high nonlinearity and this greatly increases the difficulty of achieving their tight control. To overcome this problem, four decentralized composition control structures, i.e., the CS_R/QR, CS_R/B, CS_D/QR, and CS_D/B structures, are proposed and compared based on the control of a Kaibel distillation column fractionating a methanol/ethanol/propanol/butanol quaternary mixture. These four composition control structures all include five composition control loops. While the four of them are employed to maintain the purity of the top, upper sidestream, lower sidestream, and bottom products, the remaining one is employed to minimize the energy consumption of the Kaibel distillation column by maintaining the composition of propanol at the first stage of the prefractionator. Dynamic simulation results show the CS_R/QR and CS_R/B structures can tightly maintain the purity of the controlled products with a small overshoot and short settling time after facing various disturbances in feed conditions, but the CS_D/QR and CS_D/B structures lead to oscillatory responses (the latter even shows divergent responses under individual disturbances). At the end of the article, some effective guides for developing composition control systems are given.