In order to increase the capacity and diminish the multiple access interference (MAI) of an ultra-wideband (UWB) system, we propose a new time-hopping/direct-sequence (TH/DS) scheme using N-ary biorthogonal pulse position modulation (BPPM). In contrast with the conventional TH/DS systems employing fixed partition of the TH slots (Shen and Ueng, Proceedings of the IEEE VTC-Spring, 2010), the proposed TH/DS system can put the start location of the TH slot in any one of Q available pulse positions within the frame. In the proposed TH/DS system, the modulation level of BPPM can be increased and the multiple access capability can be improved without degrading the system performance. Compared with the existing TH-UWB system that employs the whole frame to carry out TH process (Shen et al. IEEE Trans. Veh. Technol. 59(2), 742-753, 2010), the proposed system has the merits of smooth power spectral density and low receiver complexity. In this article, we also derive the probability distribution of MAI for each correlator's output of the proposed TH/DS system based on the analytic characteristic function technique. In order to verify the correctness of the performance analyses and to demonstrate the effectiveness of the proposed TH/DS system, some simulation results are given in both the additive white Gaussian noise channel and the realistic UWB fading channels. From the simulation results, we find that the proposed TH/DS system outperforms the conventional TH/DS scheme.