In this work, the effect of cellulose nanofiber (CNF) on the mechanical properties of long pineapple leaf fiber (PALF)-reinforced epoxy composites was investigated. The content of PALF was fixed at 20 wt.% and the CNF content was varied at 1, 3, and 5 wt.% of the epoxy matrix. The composites were prepared by hand lay-up method. Comparison was conducted between CNF-, PALF- and CNF–PALF-reinforced composites. It was found that the introduction of these small amounts of CNF into epoxy resin caused very small effects on flexural modulus and strength of neat epoxy. However, impact strength of epoxy with 1 wt.% CNF increased to about 115% that of neat epoxy, and, as the content of CNF increased to 3 and 5 wt.%, the impact strength decreased to that of neat epoxy. Observation of the fractured surface under electron microscope revealed the change in failure mechanism from a smooth surface to a much rougher surface. For epoxy containing 20 wt.% PALF, both flexural modulus and strength increased significantly to about 300% and 240% that of neat epoxy. The composite impact strength increased to about 700% that of the neat epoxy. For hybrid systems containing both CNF and PALF, there were few changes observed in both flexural modulus and strength compared to the PALF epoxy system. However, much improvement in impact strength was obtained. By using epoxy containing 1 wt.% CNF as the matrix, the impact strength increased to about 220% that of 20 wt.% PALF epoxy or 1520% that of neat epoxy. It thus could be deduced that the spectacular improvement in impact strength was due to the synergistic effect of CNF and PALF. The failure mechanism leading to the improvement in impact strength will be discussed.