Fossil fuel power plants are a significant contributor to global carbon dioxide (CO2) and nitrogen oxide (NOx) emissions. Accurate monitoring and effective reduction of these emissions are crucial for mitigating climate change. This systematic review examines the current state of research on the application of machine learning techniques in evaluating the emissions from fossil fuel power plants. This review first briefly introduces the continuous emission monitoring (CEM) systems and predictive emission monitoring (PEM) systems that are commonly used in power plants and highlights that machine learning models can significantly improve PEM systems through their capability to process and interpret large datasets intelligently to transform traditional emission monitoring systems by enhancing their precision, effectiveness, and cost-efficiency. Compared to previously published review articles, the key contribution and innovation in this present review is the discussion of machine learning models in CO2/NOx emissions according to the different algorithms used, including their advantages and disadvantages in a systematic way, which aims to help future researchers to develop more effective machine learning models. The most popular machine learning model includes reinforcement learning, a forward neural network, a long short-term memory neural network, and support vector regression. While each model method has its own advantages and disadvantages, we noted that training data quality, as well as the proper selection of model parameters, plays an important role. The challenges and research gaps, such as model transferability, a deep understanding of the physics of CO2/NOx emissions, and the availability of high-quality data for training machine learning models, are identified, and recommendations as well as potential future research directions to address these challenges are proposed and discussed.