Reported here is a characterisation of a series of NDI-thiophene copolymers with 1, 2, 3 and 4 thiophene units synthesized using Stille polycondensation of dibromo-naphthalene diimide and the trimethylstannylthiophene monomers. The effect of extension of the thiophene donor group is studied in terms of structure-charge transport correlation. The influence of side chains located on the thiophene units of copolymers with 2 and 4 thiophene units per monomer is also investigated. Charge transport of both signs is studied experimentally in field-effect transistors. Microstructural data obtained by near-edge x-ray absorption fine structure (NEXAFS) and grazing incidence wide-angle x-ray scattering (GIWAXS) is supported by AFM topography scans. UPS and UV-Vis spectroscopy data are employed in measurement of energy levels and changes with annealing temperature are also discussed. Most of the polymers reach excellent electron as well as hole mobility with one copolymer (NDI-T4) exhibiting an especially balanced ambipolar charge transport of 0.03 cm2V-1s-1. An odd-even effect in hole mobility is observed with higher values for polymers with even number of thiophene units. The reported findings indicate that the final charge transport properties are a result of the interplay of many factors, including crystallinity, planarity and linearity of chain, spacing between acceptor units and packing of solubilizing branched side chains.