Network coding (NC) has recently attracted intense research focus for its potential to provide network throughput enhancements, security and reduced network congestions, improving in this way the overall network performance without requiring additional resources. In this chapter, the all-optical physical-layer network coding (AOPNC) technique is presented, focusing on digital encoding schemes that are based on optical XOR logical gates. It is also discussed how digital AOPNC can be implemented between sub-carrier-modulated (SCM) optical signals in radio-over-fiber (RoF) networks, circumventing the enhanced complexity arising by the use of SCM signals and the asynchrony that might exist between the data arriving at the encoding unit. AOPNC demonstrations are described for simple on/off keyed (OOK)-SCM data signals, as well as for more sophisticated higher-order phase modulation formats aiming to further improve spectrum efficiency and transmission capacity.