Adequate identification and quantification of chemically diverse mixtures containing non-volatile components is far from straightforward, particularly since they are no longer compatible with gas chromatography–mass spectrometry (GC-MS) analysis. The lack of suitable analytical techniques for such mixtures is currently hampering research which could advance evolutions towards a circular economy, e.g., the replacement of petrochemical aromatics by green alternatives produced via lignin depolymerization. Two-dimensional liquid chromatography (LCxLC) is capable of separating these non-volatiles, but lacks the versatility and general ease-of-use of GC-MS in electron impact (EI) mode. Therefore, in this project, a novel analysis technique, which combines the capacity of gel permeation chromatography (GPC) to separate non-volatiles with the unmatched separation and identification power of two-dimensional gas chromatography (GC×GC-MS) will be developed. First, GPC and pyrolysis-GCxGC-MS will be coupled in an offline mode and the parameters of both techniques will be optimized. Subsequently, the hardware will be integrated into a single configuration with online hyphenation. In parallel, an innovative visualization and interpretation method for the huge amounts of data generated with the envisioned analysis technique will be developed. Finally, the analytical power of the novel technique in the intended application will be showcased in a proof-of-concept case study.