To improve current matching in a tandem solar cell, a strain-compensated InGaAs/GaAsP multiple quantum-wells (MQWs) structure was grown within the middle GaAs PN junction, using metal organic vapor phase epitaxy (MOVPE) on GaAs substrate. Aiming at an accurate design of adsorption edge and precise control of crystal quality in MQWs, post- and in situ characterization was applied in such a fabrication process. Here, we report some applications of some post-characterization such as: X-ray scanning and reciprocal mapping in clarifying composition and crystal quality in these structures; photoluminescence (PL) and FTIR in determining adsorption edge and even indicate some irradiative recombination features as well. By employing an in situ optical surface reflectivity measurement, we established a way of and evaluating an instant of strain relaxation in the course of MOVPE, which deteriorates crystal quality significantly. When strain balancing was incomplete, surface reflectivity dropped during the growth of MQWs, indicating lattice relaxation. The accumulated strain, which is defined as the average strain per period of QW multiply the number of stacking for MQWs , was roughly constant for all the MQWs samples in our experiment. Therefore, it may indicate that this overall strain may be used as a tentative criterion of critical value for lattice relaxation or to predict the maximum number of MQWs for a given value of the average strain per QW period. Combining both post and in situ characterizations, we can effectively adjust the overall strain to get defects free growth for MQWs, and also significant features can be observed for better understanding the heterostructure management.