The influence of olivine-type blending with LiNi0.90Co0.05Al0.05O2 (NCA) powders and electrochemical properties were investigated by means of XRD, SEM, and charge-discharge tests. The rate capability of the pristine NCA electrode showed the capacity retentions of 79.9, 73.3, and 63.8% at 1.0, 2.0, and 5.0 C, respectively. After blending, the capacity retentions of the mixtured sample were increased to 86.8, 81.1, and 73.7% at 1.0, 2.0, and 5.0 C, respectively. The higher capacity retention and superior rate capability of blended sample can be ascribed to the improved energy density and network effect of nanofibers.