Off-line pyrolysis TMAH-GC-MS (thermochemolysis) and solid-state 13C NMR spectroscopy were applied for the direct molecular characterization of composted organic biomasses after 60, 90, and 150 days of maturity. Off-line thermochemolysis of both fresh and mature composts released various lignin-derived molecules, the quantitative measurement of which was used to calculate structural indices related to compost maturity. These indicated that most of the molecular transformation occurred within the first 60 days of the composting process, whereas slighter molecular variations were observed thereafter. Both 13C NMR spectra and offline programs suggested that the process of compost maturity was characterized by a progressive decrease of alkyl components, whereas cellulose polysaccharides appeared to be more resistant and began to be transformed at a later composting period. The main components of the final mature compost were lignocellulosic material and hydrophobic alkyl moieties, in as much as that commonly found in well-humidified organic matter of soils and sediments. The persistence of untransformed lignin-derived products and di- and triterpenoids throughout the maturity period suggested that these molecules are useful markers to both evaluate compost origin and trace its fate in the environment. Thermochemolysis provided the same characterization of molecules either unbound or bound to the compost matrix as that reached by a previously applied sequential chemical fractionation of the same compost materials, thereby indicating that thermochemolysis is a more rapid and equally efficient tool to assess compost molecular quality.