Firstly, a diamine monomer, 4-(4-(tert-butoxy)phenyl)-2,6-bis(4-aminobenzene) pyridine (TPAP) was synthesized by two-step reaction from 4-tert-butoxybenzaldehyde and 4-nitroacetophenone as raw material. Secondly, polyamic acids (PAAs) were prepared via the "two-step method" solution polycondensation based on TPAP with five kinds of commercial aromatic tetracarboxylic dianhydride, such as pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 3,3′,4,4′-diphenylethertetracarboxylic dianhydride (ODPA), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4′-(hexafluoro isopropylidene)diphthalic anhydride (6FDA). The intrinsic viscosity of polymeric acid was also measured in the range of 0.31 dL/g to 1.55 dL/g by Ubbelohde under 25 ℃. Lastly, a series of polyimides (PIs) containing bulky tert-butoxyphenyl groups and heterocyclic pyridine ring units were prepared by the thermal imidization of PAAs. PIs show a good solubility in polar solvents. Furthermore, PIs have outstanding thermal properties with a glass transition temperature (Tg) in the range of 325～349 ℃ and the temperature of thermal mass loss is all above 535 ℃. The char yield at 800 ℃ is all over than 63%. Moreover, polymers also show an excellent hydrophobicity with the contact angle in the range from 84.1° to 91.0° and the water absorption in the range from 0.66% to 0.99%.