Three samples of GaAs/AlAs multiple-quantum wells with different quantum well widths andδ-doped with Be ac-ceptors at the well center were grown on (100) GaAs substrates by molecular beam epitaxy. Polarized Raman spectra were recorded on the three samples at temperatures in a range of 4–50 K in a backscattering configuration. The two branches of coupled modes due to the interaction of the hole intersubband transitions and the quantum-well longitudinal optical (LO) phonon were observed clearly. The evaluation formalism of the Green function was employed and each lineshape of the Raman spectrum of the coupled modes was simulated. The dependence of the peak position of Raman shifts of the two coupled modes as well as the quantum-well LO phonon on the quantum-well size and measured temperature were given, and the coupling interaction mechanism between the hole subband transitions and the quantum-well LO phonon was researched.