We present the structural (XRD and Raman) and electrochemical properties of various oxides of the cobaltate family (with the alpha -NaFeO2-type structure) grown by solid-state reaction, wet chemistry and film deposition techniques. It is shown that synthesis greatly affects the electrochemistry and cycle life characteristics of these layer structured cathode materials. HT-LiCoO2, LT-LiCoO2, doped LiCo1-yAlyO2 and LiCoO2 films are investigated.