A method of off-line coupling of thin layer chromatography with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (TLC/MALDl-TOF MS) was used to study a synthetic procedure that produces well-defined hydroxyl-end-capped polymers. The TLC separation is based on the structure of the end group of the polymer and is not affected by the degree of polymerization. MALDI-TOF mass spectral analysis of these TLC fractions confirmed their structures.