In densely-populated cities or indoor environments, limited visibility to satellites and severe multipath effects significantly affect the accuracy and reliability of satellite-based positioning systems. To meet the needs of “seamless navigation” in these challenging environments an advanced terrestrial positioning system is under development. This system is based upon Ultra-Wideband (UWB) technology, which is a promising candidate for this application due to good time domain resolution and immunity to multipath. This paper presents a detailed analysis of two key aspects of the UWB signal design that will allow it to be used as the basis of such a high performance positioning system: the modulation scheme and the multiple access technique. These two aspects are evaluated in terms of spectral efficiency and synchronisation performance over multipath channels. Thus this paper identifies optimal modulation and multiple access techniques for a long range, high performance terrestrial positioning system using UWB.