We have studied Raman scattering from longitudinal‐ and transverse‐optical (LO and TO) phonon modes in InAsxSb1–x epilayers grown on GaAs(001) substrates with various arsenic compositions (x). InSb‐like and InAs‐like LO and TO phonon modes of the epilayers are observed. We find that the peak intensity ratio of the InAs‐like LO to TO‐mode decreases for x < 0.6 while it increases for x > 0.6. This intensity ratio change is attributed to two‐ and three‐dimensional (2D and 3D) growth mode of the epilayers using atomic force microscopy. Further, the intensity ratio depends on the root mean square surface roughness of the alloy. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)