Structural and optical properties of Si-doped as well as nominally undoped GaInP epilayers grown on Germanium substrates by metal-organic chemical vapor deposition have been investigated by high resolution transmission electron microscope and photoluminescence (PL). Si incorporation results in an increased inner band PL transition and a blue shift of PL energy with increasing temperature, which arises from the trapping states around Ge-GaInP interface due to Ge diffusion to GaInP epilayer as well as Si doping. For the inter band PL transition, a competition between the emission processes near the band edge and in the ordered GaInP domains is responsible for the inverted S shape temperature dependence of PL peaks. By analyzing the time-resolved PL results, we attribute this emission near the ordered states to the localized states due to the potential fluctuation, which is induced by the compositional inhomogeneity of Ga and In in the partially ordered GaInP.