An integrated advanced supercritical coal-fired oxyfuel power plant with a novel cryogenic CO2 separation and compression technology for high purity CO2 to suit injection for enhanced oil recovery purposes is investigated. The full process is modelled in Aspen Plus® consisting of: an Air Separation Unit (ASU), an Advanced Supercritical Pulverised Fuel (ASC PF) power plant with a bituminous coal as feedstock, a steam cycle, and a Carbon dioxide Purification Unit (CPU). The proposed CPU process accommodates a distillation column with an integrated reboiler duty to achieve a very high purity CO2 product (99.9%) with constrained oxygen levels (100 ppm). This work presents a detailed analysis of the CO2 separation and compression process within the full power plant, including effective heat integration to reduce the electricity output penalty associated with oxyfuel CO2 capture. The results of this analysis are compared with previous studies and indicate that the combined application of process optimisation in the CPU and advanced heat integration with the power plant offer promising results: In this work a high purity CO2 product was achieved while maintaining 90% capture for a net plant efficiency of 38.02% (LHV), compared with a thermal efficiency of 37.76% (LHV) for a reference simulation of an ASC PF oxy-fired plant with advanced heat integration, providing a lower purity CO2 product.