As a newly-emerged paradigm in the networking techniques, physical-layer network coding (PNC) [1, 5] takes advantage of the superimposition of the electromagnetic waves, and embraces the interference which was typically deemed as harmful, by performing exclusive-or mapping. Therefore, the spectral efficiency is utilized, which in turn boosts the network throughput. In the classical 2-way relay channel (2-WRC), PNC only spends two channel uses for the bi-directional data exchange. However, one challenge for such a paradigm is that the singular fading states in the uplink of 2-WRC, might result in ambiguity for decoding the network coded symbol. One major focus of this thesis is to address the fading issue for PNC in the 2-WRC. Another fundamental challenge for PNC is to extend the PNC from the 2-WRC to a multi-user network such as the multi-way relay channel (M-WRC) or the hierarchical wireless network (HWN). To tackle these two fundamental challenges of PNC, several solutions are proposed in this thesis, which are summarized as follows: First, we introduce two efficient fading correction strategies, i.e., the rotationally-invariant coded modulation and the soft-bit correction. Second, a novel multilevel coded linear PNC scheme with extended mapping for the Rayleigh fading 2-WRC is proposed. Third, we design a new type of linear PNC for the Rayleigh fading 2-WRC, based on rings. We refer to such design as linear PNC over the hybrid finite ring. Fourth, we redesign PNC for the HWN, which facilitates the multi-user data exchange. To combat the co-channel interference introduced by multi-user data exchange, two efficient interference exploitation strategies based on network coding are proposed: 1) PNC with joint decoding; and 2) analogue network coding with interference-aware maximum likelihood detection. Finally, we propose a multilevel coded LPNC for the data exchange in the M-WRC
