In order to improve the PI resin’s processability and thermal properties, a novel diamine monomer bis(p-aminophenylethynyl)dimethylsilane was designed and synthesized by introducing silicon and alkyne groups in this paper. And a new thermosetting polyimide resin SiOPI with silicon and alkynyl structures in the main chain was prepared using 4,4′-oxobis (phthalic anhydride) (ODPA) as the dianhydride monomer with this diamine monomer. The structures of the diamine monomer and the polyimide were characterized by H nuclear magnetic resonance spectroscopy (1H NMR), Fourier transform infrared spectroscopy (FT-IR), mass spectrometry (MS), and X-ray diffraction (XRD), respectively. The incorporation of silyl groups into the PI increases the flexibility of the resin and provides good solubility and processability. The SiOPI is well soluble in DMF, DMSO and THF. The resin has a viscosity of less than 200 Pa·s at 50–88°C and has a wide processability range. By virtue of the introduction of alkyne groups, the cured polyimide forms dense reticulated structures, analogous to the benzene ring, giving the resin excellent heat resistance and mechanical property. The glass transition temperature (Tg) of SiOPI reached 367°C, and the heat loss temperature at 5% (Td5) is 540.9°C, the heat loss temperature at 10% (Td10) is 592.2°C, and the residual carbon rate at 800°C (R800°C) is 65.76% in a nitrogen atmosphere. The tensile strength of c-SiOPI is 257.6 MPa at room temperature and 232.9 MPa with a retention rate of 90.41% at 300°C, respectively.