Fiber reinforcement in polymer matrix contribute significant role in improving mechanical and tribological behavior of any composite for friction application. Hence such composites are developed by selecting suitable matrix and reinforcement materials. In the present study three frictional composite materials were prepared by varying basalt fiber, aramid fiber and hybrid of both theses fibers. Namely Basalt Fiber reinforced composite (BFRC), Aramid Fiber reinforced composite (AFRC) and Hybrid of these fibers reinforced Composite (HFRC), with polyimide matrix. The other ingredients were mixed in constant proportions to enhance the frictional property of the composites and specimens were prepared using hot compression molding machine. The pin-on-disc testing was carried out with different loading condition of 20, 30 and 40 N and varying sliding velocities of 150, 200 and 250 rpm to understand the effect of these parameters on coefficient of friction and the wear rate of specimens. Based on results, contour were developed using Minitab software. HFRC shows the best tribological characteristics compared to BFRC and AFRC. The contact temperature is less for HFRC due to the good heat conduction by hybrid fibers. The thermal stability and the degradation of composites were study from Differential scanning calorimetry (DSC) and Thermogravimetric Analysis (TGA) respectively. It is observed that HFRC has better thermal stability. The Scanning Electron Microscopy images shows better bonding of matrix and fiber for HFRC compared to other composites and various mechanisms were identified along the wear regime areas.