A series of novel soluble polyimides was synthesized from commercially available 2,4,6-triaminopyrimidine (TAP), 2,2-bis(3,4-dicarboxylphenyl) hexafluoropropane dianhydride (6FDA), α,ω-aminopropylpoly(dimethylsiloxane) and 1,3-bis(3-aminophenoxy)benzene. TAP is the branched monomer, and polymerization process had been improved in three ways by using TAP to prepare soluble polyimides. The polyimides were characterized by Fourier transform infrared spectra, proton nuclear magnetic resonance, ultraviolet–visible spectrometer analysis, wide-angle X-ray diffraction, and size-exclusion chromatography with multiangle laser light-scattering detection. The branched polyimides showed excellent solubility both in strong polar solvents and in common low-boiling point solvents. Differential scanning calorimetric and thermogravimetric analyses showed high glass transition temperatures and excellent thermal stability for branched polyimides with moderate content of TAP. Polyimide membranes were formed at relatively low temperature, and the mechanical properties were tested. These results ensure that soluble polyimides with moderate content of TAP showed outstanding combined features and are desirable candidate materials for advanced applications.