Raw primary sewage sludge (Wastewater Treatment Plant of Krotoszyn, SW Poland) and its mixtures with 3%d, 6%d, 9%d, 12%d and 24%d of calcium hydroxide were stabilised for 1 and 35 days. Changes of the sludge physicochemical properties and molecular composition, caused by alkaline agent in course of stabilisation process, are recognised. A basic physicochemical data on the sludge cake and filtrate after 1 and 35 days of stabilisation process are given. Soxhlet extracts from the sludge cakes stabilised for 35 days as well pyrolysis and pyrolysis in situ methylation (using tetramethylammonium hydroxide-TMAH) products of respective pre-extracted cake residues were analysed by gas chromatography-mass spectrometry (GC-MS). Increase of calcium hydroxide concentration in the sludge mixture causes enhanced ammonia release, preferential hydrolyses of fats and proteins from the sludge macromolecular network and transformation of free fatty acids contained in the sludge lipids, as well as these released hydrolytically, to their calcium salts. The sewage sludge stabilisation with calcium hydroxide has no effect on homological assemblage and content of unbound stanol and sterol compounds in the sludge lipids and these bound into macromolecular network. Biogenic n-alkanes and anthropogenic linear alkylbenzenes were detected as minor components in the lipids and pyrolytic products from the pre-extracted cake residue, respectively. The alkaline agent used for the sludge stabilisation accelerates equilibration of the process and reduces content of pathogenic microorganisms.