Organic semiconductors (OSCs) are characteristic of long spin-relaxation lifetime due to weak spin-orbit interaction and hyperfine interaction. However, short spin diffusion length and weak magnetoresistance (MR) effect at room temperature (RT) was commonly found on spin valves (SVs) using an organic spacer, which should be correlated with low carrier mobility of the OSCs. Here, N-type semiconducting polymer P(NDI2OD-T2) with high carrier mobility is employed as the spacer in the SV devices. Exceedingly high MR ratio of 90.0% at 4.2 K and of 6.8% at RT are achieved, respectively, via improving the interface structure between the polymer interlayer and top cobalt electrode as well as optimal annealing of manganite bottom electrode. Furthermore, we observe spin dependent transport through the polymeric interlayer and a large spin diffusion length with a weak temperature dependence. The results indicate that this polymer material can be used as a good medium for spintronic devices.