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Header processing in all-optical domain in ultrafast photonics network is challenging issue. In this paper, we present modelling and simulation of all-optical header processing based on pulse position modulation (PPM) format for 100 Gbit/s packet-switched network composed up to 256 nodes. Both the header address codeword (8-bit) and the routing table are converted into PPM format, where the later offers reduced entries compared with the existing routing table. Simulation results show that matching of 256 8-bit header address with routing table entries can be performed effectively and as fast as possible using all optical AND gates.