This paper presents experimental investigations on high precision localization methods of body-worn miniature antennas using ultra-wideband technology in line-of-sight conditions. Time of Arrival data fusion and peak detection techniques are implemented to estimate the three-dimensional location of the transmitting tags in terms of x, y, z Cartesian coordinates. Several pseudo-dynamic experiments have been performed by moving the tag antenna in various directions and the precision with which these slight movements could be resolved has been presented. Some more complex localization experiments have also been undertaken, which involved the tracking of two transmitter tags simultaneously. Excellent 3D localization accuracy in the range of 1-4 cm has been achieved in various experiment settings. A novel approach for achieving sub-centimetre 3D localization accuracy from UWB technology has been proposed and demonstrated successfully. In this approach, the phase centre information of the antennas in a UWB localization system is utilized in position estimation to drastically improve the accuracy of the localization measurements to millimetre levels. By using this technique, the average localization error has been reduced by 86%, 31% and 72% for the x, y and z axes coordinates, respectively.