Oligomers of poly(diethyl 3-hydroxyglutarate), an aliphatic hyperbranched polyester, have been prepared via a titanium(IV) butoxide catalysed step growth condensation process. The characterisation of the products depends on MALDI-TOF mass spectrometry; this study establishes that the incident laser power has a marked effect on the distribution of peak intensities in the spectra observed for these systems. High laser powers can initiate scissions in the polymer structure, whilst at lower incident laser power it is very difficult to define what constitutes a "representative spectrum".