In this paper, we study the capacity and performance of nonorthogonal pulse position modulation (NPPM) for Ultra-Wideband (UWB) communication systems over both AWGN and IEEE802.15.3a channels. The channel capacity of NPPM is determined for a time-hopping multiple access UWB communication system. The error probability and performance bounds are derived for a multiuser environment. It is shown that with proper selection of the pulse waveform and modulation index, NPPM can achieve a higher capacity than orthogonal PPM, and also provide better performance than orthogonal PPM with the same throughput.