The quantification of interdiffusion processes in the interfaces of GaAs quantum wells. with thickness ranging from one to six atomic layers, grown by atomic layer molecular beam epitaxy in a GaP matrix is addressed. The atomic row positions have been determined from high resolution transmission electron microscopy images. The distortion of distances and angles between neighboring rows with respect to those expected in the strained structure has been related to changes in chemical composition. This method appears more efficient for this system than other methods based on the analysis of the atomic row contrast. Results show that interdiffusion occurred at the GaAs/GaP interfaces. The arsenic profiles in the quantum well suggest that the main contribution of interdiffusion comes from atomic exchange. The experimental profiles have been fitted to a simple model of segregation giving segregation coefficients around 0.45. The results are compared to simulations based on Raman measurements performed on the same samples. (C) 2004 American Vacuum Society.