Coal power plants have been a major source of undesirable emissions. Despite the technological advancements in renewable energies, coal units are still in-service in many developed and developing countries due to their reliability, adequacy, and flexibility for power delivery. There are some promising technologies for cleaner operation during power production from coal, including supercritical boiler (SC) design and carbon capture and storage (CCS), however, the challenging in innovating effective methods is still open to expand the boundary of knowledge in this speciality. This paper introduces a novel and simple method for reducing CO2 emissions and improving the dynamic responses of a 600 MW SC coal power plant by Artificial Neural Network (ANN) technique. A wide-range data-driven feedforward ANN model has been identified and verified for the various operations recorded as closed-loop data-sets, which covers all situations of startup, once-through mode, and even emergency shutdown of the unit. The closed-loop SC plant model has been augmented with an inverse multivariable coordinate NN controller, developed by analogous learning algorithm to improve the plant automation. With precisely selected setpoints, as operational rules, of temperature, pressure, and earliest possible power demand signals, the automated SC plant has been capable to operate with lower coal consumption - and thus lower emissions – than the existing operation strategy during startup, normal operation, and emergency shutdown modes. The improvement in dynamic responses have been quantified through simulations with comparison with existing performance, which have resulted in an overall average reduction of 2.143 Kg/s in coal consumption.