Metalorganic vapor phase epitaxy (MOVPE) is used to grow unicompositional quantum-well (QW) structures, in which the QW and barrier layers are composed of ordered and disordered GaInP, respectively. Transmission electron dark-field micrographs reveal abrupt interfaces between highly ordered QWs and disordered barriers, with no evidence of defect formation. Low-temperature photoluminescence from the structures exhibits relatively broad emission peaks, with emission energy increasing with decreasing QW thickness. The dependence of emission energy on well thickness can be described by a finite square well model only when a type-II band alignment is taken for the heterostructure, in which the conduction band edge of the ordered GaInP QW lies about 135-150 meV below that of the disordered barrier material. These results demonstrate a high degree of control over the ordering process in MOVPE, such that quantum size effects can be realized solely through disorder-order phenomena. Further, the data provide strong support for a type-II (spatially indirect) recombination transition between ordered and disordered GaInP.