This paper describes the development and characterisation of a novel type of composite Z-pin able to accommodate large deformation without exhibiting fibre failure. Three types of pseudo-ductile Z-pins are fabricated by means of micro-pultrusion of polybenzoxazole (PBO) fibres. Namely, unidirectional PBO fibre (uPBO) Z-pins in combination with a ductile (uPBO/DCT) and a brittle (uPBO/BT) matrix system are developed, together with a twisted PBO fibre Z-pin in combination with a ductile matrix (tPBO/DCT). Single pin bridging tests are carried out across the full mode mixity range from mode I (Φ = 0) to mode II (Φ = 1). The tests reveal that uPBO-based pins are able to pull out throughout the full mode mixity range, regardless of the ductility of the pin matrix. uPBO/DCT pins exhibit a 20-fold increase in energy dissipation per pin than traditional carbon fibre/bismaleimide (CF/BMI) pins at load mode mixities higher than Φ = 0.9. The mode I behaviour of all pins considered is comparable. All PBO pins exhibit an apparent delamination toughness enhancement superior to CF/BMI at mode mixities above Φ = 0.2, with a ductile matrix increasing the average energy dissipated per pin by a further 2–8 %.