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Summary form only given. Electron distribution among subbands in semiconductor quantum wells (QWs) has become of great interest since the demonstration of population inversion and lasing action in the quantum cascade laser. We applied two color mid-IR picosecond pump-probe spectroscopy for the study of electron dynamics in a QW three-level structure. Our samples, grown by molecular-beam epitaxy on a semi-insulating InP substrate, consist of 40 10-nm-thick GaInAs wells separated by 10 undoped AlInAs barriers.