Undoped Ga0.5In0.5P has been successfully grown by organometallic vapor‐phase epitaxy on GaAs substrates with a free‐electron concentration of 1016cm−3and a mobility of 1050 cm2/V s in nominally undoped material. The distribution coefficient of indium in the growth of Ga0.5In0.5P is nearly to unity. Bothn‐ andp‐type carrier concentrations of up to 1019cm−3have been obtained in the present study. Diethyltelluride and silane are used asn‐type dopants. Dimethylzinc is used as thep‐type dopant. Te is a very efficient dopant with a distribution coefficientkTe=54. The photoluminescence (PL) intensity increases with Te doping level to a maximum atn=2×1018cm−3. The silicon distribution coefficient is temperature dependent, due to the incomplete pyrolysis of silane at the growth temperature. Si‐doped Ga0.5In0.5P has a lower PL efficiency than Te‐doped samples and is not strongly correlated with carrier concentration. The incorporation efficiency of Zn is low, withkZn=3.8×10−3, due to the high vapor pressure of Zn at the growth temperature. The PL intensity of Zn‐doped Ga0.5In0.5P also increases with Zn doping level to a maximum atp=2×1018cm−3and is comparable to the optimum Te‐dopedn‐type Ga0.5In0.5P. Only a single band‐edge PL peak is observed in all cases.