A new Ga0.5In0.5P light-emitting diode (LED) with order/disorder/order (DOD) structure has been fabricated by metalorganic chemical vapor deposition. Growth temperature and dopant concentration were successfully used as growth parameters to obtain a heterojunction-equivalent structure. From the 77 K photoluminescence measurement, three peak energies of the DOD structure can be resolved clearly. It is shown that the DOD structure is equivalent to the double-heterojunction structure. The wavelength of the LED occurring at 667 nm coincides with the ordered active layer emission. The light intensity of the DOD LED is seven times stronger as compared with that of the homojunction disordering LED at the injection current of 10 mA. These results demonstrate that the DOD structure can provide good electrical and optical confinements and can be served as heterojunction-equivalent applications.