In this work, we systematically investigated the mechanical and electronic properties of a range of high performance conjugated polymers. We use state-of-the-art characterisation tools such as small-angle neutron scattering technique to investigate the rigidity of these highly fused polymers. Highly sensitive absorption techniques, including the photothermal deflection spectroscopy(PDS) technique is used to correlate the microstructure property of these materials to their energetic disorder. Charge transport property of these newly emerged materials is investigated by OFETs characterisation. An alignment setup is built to fully utilise the rigid backbone of these fused polymers, align polymer chains along a certain direction to improve the directional charge transport property.