In this work, an oxidatively degraded polypropylene (DgPP) was studied as a novel coupling agent for fibrous cellulose (FC)/polypropylene (PP) composite. An optimal preparation time of PP thermal oxidative degradation was 18 h at 130 °C, and the DgPP had functional groups such as γ-lactone and acid groups. The spherulite observation of the DgPP suggested miscibility for the undegraded PP. The addition of the DgPP presented the transparency improvement of FC/PP composite, and this behavior was found to be originated from the grafted DgPP, which was produced by the esterification reaction between the of FC and the DgPP. The scanning electron microscope (SEM) observation showed that the grafted DgPP coated the FC surface, and the tensile strength of the FC/PP composite increased by an appropriate amount of the DgPP addition. These results suggested that the DgPP was suitable for the coupling agent of FC/PP composite.