In-situ characterization is one of the most powerful techniques to improve material quality and device performance. Especially in view of highly efficient tandem solar cells this is an important issue for improving the cost-performance ratio. Optical techniques are suitable characterization methods, since they are non-destructing and contactless. In this work, we measured the power dependence of photoluminescence (PL) from the InGaP and GaAs subcells of an industry-standard triple-junction solar cell. High luminescence yields enhance the luminescence coupling, which was directly verified by time-resolved PL measurements. We present a new method to determine the internal luminescence efficiencies of InGaP and GaAs subcells with the aid of luminescence coupling. High luminescence efficiencies of 90% for GaAs and more than 20% for InGaP were found, which suggest that the material quality of the grown GaAs layer is excellent while the intrinsic luminescence limit of InGaP is still not reached even for high excitation conditions. The PL method is useful for probing the intrinsic material properties of the subcells in flat band condition, without influence of transport. Since no calibration of absolute PL is required, a fast screening of the material quality is possible, which should be extremely helpful for the solar cell industry.