Poly(dimethylsiloxane) was studied by laser Raman spectroscopy and differential scanning calorimetry. The Si-O-Si skeletal mode at 489 cm(-1) and the C-Si-C deformation bands at 188 cm(-1) and 158 cm(-1) were studied as functions of temperature from ambient to -130 degrees C, and effects of temperature interpreted in accordance with results from thermal analysis.