Coal combustion produces by-products such as fly ash and pond ash, which contain valuable trace elements and rare earth elements (REYs), including Ga, Sc, La, Ce, and Nd. This study reveals the partitioning of these elements in the combustion by-products from NTPC Korba power plant, which uses coal from Gevra mines in Chhattisgarh, India. Results indicate that the ash primarily consists of SiO2, Al2O3, and Fe2O3, meeting Indian standards for use as a pozzolana in cement and concrete. In pond ash, Ba, Sr, and Cr showed the highest trace element concentrations, while La, Sm, Ce, Nd, and Y were the most abundant REYS, totalling 211–383 mg/kg. Fly ash had higher REY concentrations, ranging from 267–401 mg/kg, with La and Ce being the most prevalent. Ga and Sc concentrations notably increased across ESP hoppers, from 32.2 to 147 mg/kg for Ga and 16.7 to 24.2 mg/kg for Sc. This study accentuates coal ash as a promising secondary source for critical elements, emphasizing the potential for efficient recovery and recycling of Ga, Sc, and REYS, which could lower production costs and reduce environmental impact.