Spinel samples of Li1.33xCo2-2xTi1+0.67xO4 crystallize in two space groups: Fd- 3 m for 0≤x≤0.40 and x=1, and P4332 for 0.50≤x≤0.875. In S.G. P4332 magnetic Co2+ ions occupy 8c sites (for x=0.75 and 0.875), or 8c, 4b and 12d sites (for x=0.50). In x=0.25 and 0.40 samples Co2+ occupy both 8a and 16d cation sites of the S.G. Fd- 3 m . Observed differences in magnetic behaviour of the samples are induced by crystallographic distribution of Co2+. Possible paths for exchange interactions in S.G. P4332 were analysed. It was found that the superexchange is the dominant exchange mechanism where Co2+ (8c)-O(24e)-Co2+(12d) path was the most important one. On the basis of the results on crystallographic distribution we suggest x=0.50 sample as potential electrode material in Li ion rechargeable batteries.