In this contribution we report on the real-time monitoring of low temperature growth of epitaxial GaxIn1-xP/GaP heterostructures on Si(100) by pulse chemical beam epitaxy, using tertiary butylphosphine (TBP), triethylgallium (TEG), and trimethylindium (TMI) as source materials. Both step-graded and continuously graded heterostructures have been investigated. The composition of the GaxIn1-xP epilayers has been analyzed by various techniques including X-ray diffraction, Rutherford backscattering, Auger, and Raman spectroscopy. Good correlation has been found between X-ray diffraction, RBS, and Vegard's law compositional analysis. We used Ppolarized Reflectance Spectroscopy (PRS) and Laser Light Scattering (LLS) to monitor the growth rate and surface morphology during growth. The information gained by these techniques has been utilized in the improvement of the surface preconditioning as well as to optimize the initial heteroepitaxial nucleation and overgrowth process. We studied the optical response to the compositional changes in the surface reaction layer (SRL) during the exposure of the surface to either sequential or synchronous pulses of TEG and TMI. The cross sectional TEM analysis indicates that the synchronous exposure results in an abrupt GaxIn1-xP/GaP interface while the sequential exposure does not which may suggest a compositionally graded interlayer formation. For heteroepitaxial GaxIn1-xP films on Si, a buffer layer of GaP is found to be necessary for optimum uniformity of the GaxIn1-xP layer. The selective growth of GaxIn1-xP on Si(001) is accessed.