A novel space survivable polyimide with a variety of desirable properties such as excellent thermal stability, high optical transparency, good mechanical strength, satisfactory break elongation, and outstanding atomic oxygen (AO) erosion resistance has been prepared by first synthesizing hyperbranched polysiloxane (HBPSi) and second incorporating HBPSi into polyimide (PI) chains via copolycondensation reactions. The 29Si nuclear magnetic resonance (29Si NMR) spectrum of HBPSi indicated that HBPSi possessed hyperbranched topology. The ground-based simulated AO exposure experiments demonstrated the mass loss of HBPSi polyimides decreased with increasing HBPSi addition and AO fluence, and it reached as low as 7.7% that of pristine polyimide when HBPSi addition was 29.7 wt % after 22 h AO exposure. Surface morphologies confirmed that pristine polyimide was significantly roughened after AO exposure while HBPSi polyimide had even less rough surface topography. During exposure of HBPSi polyimide to AO, the organic polyimide of the surface was first degraded and a silica protective layer eventually formed, which enabled the surface to be "self-healing". It is this passivation layer that prevents the underlying polymer from additional erosion. The whole preparation process of HBPSi polyimide is moderate, low-cost, environmentally friendly, and suitable for industrialized mass production, which contributes this novel material to a "drop-in" replacement for the widely used Kapton on spacecrafts functioning in space environment.