The combination of gradient HPLC, 2D chromatography, and MALDI-TOF MS facilitated the analysis of the various distributions of phthalic acid/propylene glycol-based model polyesters. Investigations of kinetic samples taken at various reaction times highlighted the subsequent differences at various stages of the polyesterification reaction in terms of molecular weight, chemical composition, and endgroups. Normal-phase gradient-HPLC analysis successfully enabled an oligomeric separation of the respective samples. Peak-splitting behavior in early eluting peaks suggested that the separation was affected by a combination of factors and not solely based on chemical composition, functionality type or degree of polycondensation. Two-dimensional chromatography provided the link between chemical composition and molecular weight distribution, confirming that the first dimension gradient HPLC separation was based on chemical composition with increasing degree of oligomerization in the second dimension. The off-line coupling of LAC with MALDI-TOF MS provided structural details in combination with improved molecular weight determination of the more homogeneous LC fractions. The study indicated that all aspects related to the model saturated anhydride system should be considered in the case of copolyester synthesis to produce industrial type polyester resins. It was shown that the present multidimensional approach provided most comprehensive structural information on the polyester system.