An attempt to understand the unusual electrochemical behaviors in (1 -x)LiNiO2.xLi(2)TiO(3) (0.05 less than or equal to x less than or equal to 0.5), an excess initial charge capacity exceeding the oxidation of transitional metal to +4 accompanying the appearance of an irreversible initial charge plateau when x reached 0.075, was performed. The decreased charge-discharge polarization after charging to 4.6 and 4.8V and increased columbic reversibility after charging to 4.6 V typically for x = 0.1 and 0.2, in contrast to charging to 4.4 V, suggested that the excess initial charge capacity possibly did not come mainly from electrolyte decomposition; while ex situ XRD results in the sample with x = 0.2 confirmed that Li+ were really extracted at the stage of the charge plateau, ruling out the possibility that electrolyte decomposition mainly accounted for the unusual electrochemical behaviors. It was inferred that the species responsible for charge compensation for the excess charge capacity must be oxygen ions in these materials, considering that Ni4+ and Ti4+ are generally impossible to be oxidized to a higher valence. Various electrochemical cycling experiments demonstrated that the sample for x = 0.05 with high resistant ability to high voltage and temperature is very promising cathode material in view of observed capacity and cycleability from a viewpoint of application. (C) 2004 Elsevier Ltd. All rights reserved.