Resin transfer molding (RTM) require phenylethynyl-terminated imide oligomers (PETIs) to exhibit low melt temperatures and better melt stability. To decrease the melt temperatures of PETIs and improve their resin transfer moldable processability, asymmetric 4,4′-diaminodiphenyl ether substituted by fluorine (F-ODA), trifluoromethyl group (3F-ODA) or phenyl group (p-ODA) were introduced. Asymmetric molecular structure and substituent groups decrease the melt temperatures of PETIs, endowing PETIs with the wider processing temperature windows and low minimum melt viscosity (<1 Pa s). These polyimides show pot lives of 30–60 min at 260–280 °C. Furthermore, the effects of backbone structure on melt fluidity of imide oligomers were discussed by the calculation of viscous activation energy (Ea,η) and analysis of Molecular Dynamics. PETI-3F and PETI-P based on 3F-ODA and p-ODA exhibit low and stable melt viscosities (<1 Pa s) at 250–270 °C and 260–270 °C for 4 h respectively, enabling the successful fabrication of carbon fiber reinforced polyimide composites via RTM process. After cured at 380 °C, the thermosets of PETI-3 and PETI-4 show high Tg of 412 °C and 402 °C and good thermal stability (Td5>550 °C). Cured PETI-3 and PETI-4 also show good mechanical properties (tensile strength >50 MPa). In comparison with p-ODA, 3F-ODA could provide PETIs with superior resin transfer moldable processability and higher heat-resistance and is more suitable to synthesize PETIs for RTM application, because of better balance between polymer segmental mobility and polymer chain packing.