We present results from the first studies of electric-field effects on optical transitions in visible-band-gap InGaP/InAlGaP multiple-quantum-well (MQW) structures. These structures, grown at 775 °C by metalorganic vapor phase epitaxy on (100) GaAs substrates misoriented 6° towards P(111〉〈111〉A, consist of nominally undoped MQWs surrounded by doped In0.49Al0.51P cladding layers to form p-i-n diodes. The Stark shifts of various allowed and forbidden quantum-well transitions were observed in bias-dependent electroreflectance spectra of In0.49Ga0.51P/In0.49(Al0.5Ga0.5)0.51P MQW samples with 10-nm-thick layers. We find the magnitude of these shifts to depend on the details of the Mg doping profile, confirming the importance of Mg diffusion and unintentional background doping in these materials. Our results show that (InAlGa)P materials are promising for visible-wavelength electro-optic modulator applications.