High-performance liquid chromatography with diode array detection (HPLC-DAD) is used to characterize mixtures from chlorophyll a degradation experiments. Overlapping chromatographic peaks are resolved by means of the heuristic evolving latent projections (HELP) method. The HELP method is a self-modelling curve resolution method. No assumptions are made about spectral and/or chromatographic peak shape. In the first step the method establishes the real noise level in the data by use of the so-called zero-component regions. This information is used to reveal selective chromatographic information and the number of chemical species at every retention time in unresolved chromatographic peaks. Utilising the selective chromatographic regions in combination with the zero-concentration windows, unique resolution into concentration profiles and spectra of the pure chemical species is accomplished. HPLC-DAD data from six chlorophyll a degradation experiments were analysed. Consistent results were obtained even with very similar spectra for six or seven overlapping chemical components.