The tensile and compressive deformation behaviour of a new type of heterocyclic rigid-rod polymer fibre, polypyridobisimidazole ＇PIPD＇ or ＇M5＇, produced by the spinning of liquid-crystalline solutions, have been studied. The Young＇s moduli and tensile strengths for the two different PIPD or M5 fibres have been determined to be greater than 300 GPa and 4 GPa, respectively. Molecular deformation in the fibres has been monitored using Raman spectroscopy and it has been shown that the peak positions of the Raman bands in the fibres are sensitive to the application of mechanical stress and strain. This has enabled a detailed study of molecular deformation to be undertaken for both tensile and compressive deformation. Full tensile-compression stress-strain curves have been derived and the compressive modulus and compressive strength of the PIPD fibres have been determined to be greater than 300 GPa and up to 1 GPa, respectively, which are both considerably higher than values for other high-performance polymer fibres. The potential use of PIPD fibres as reinforcing fibres in high-performance composites is discussed.