The molecular characterization of organic materials in samples from artworks and historical objects traditionally entailed qualitative and quantitative analyses by HPLC and GC. Today innovative approaches based on analytical pyrolysis enable samples to be analysed without any chemical pre‐treatment. Pyrolysis, which is often considered as a screening technique, shows previously unexplored potential thanks to recent instrumental developments. Organic materials that are macromolecular in nature, or undergo polymerization upon curing and ageing can now be better investigated. Most constituents of paint layers and archaeological organic substances contain major insoluble and chemically non‐hydrolysable fractions that are inaccessible to GC or HPLC. To date, molecular scientific investigations of the organic constituents of artworks and historical objects have mostly focused on the minor constituents of the sample. This review presents recent advances in the qualitative and semi‐quantitative analyses of organic materials in heritage objects based on analytical pyrolysis coupled with mass spectrometry. Analytical pyrolysis is experiencing previously unexplored potential, thanks to recent instrumental developments. Recent advances in the heritage field enable the investigation of several organic materials in artistic and historical objects that are macromolecular in nature, or which undergo polymerization upon curing and ageing, by strategies based on analytical pyrolysis coupled with mass spectrometry.