The precipitation behavior of a novel Ni-Fe-based superalloy developed for advanced ultra-supercritical (A-USC) coal-fired power plant applications during high-temperature aging treatment was investigated. The results showed that the major precipitates in the novel alloy were randomly distributed MC carbides, M23C6 carbides at grain boundaries, and the γ′-Ni3 (Al, Ti) phase in grain interiors after aging. MC remained relatively stable during both short-term and long-term aging. M23C6 quickly precipitated and exhibited a discrete distribution at grain boundaries during short-term aging, and partly developed into continuous films during long-term aging. After uniform precipitation, the shape of γ′ remained spherical, and the size kept increasing with aging time according to the Lifshitz–Slyozov–Wagner (LSW) model. The hardness of the novel alloy was mainly associated with the precipitation behavior of γ′; as γ′ gradually precipitated, the hardness steadily increased; after complete precipitation, as the size of γ′ increased, the hardness first increased and then decreased, reaching the peak hardness when the average radius of γ′ achieved the critical size. In addition, the novel alloy exhibited abnormal coarsening behavior at grain boundaries during both short-term and long-term aging. The coarsened grain boundaries were actually precipitate-free zones (PFZs) and the coarsened and elongated rod-like particles inside were identified as γ′ precipitates. The mechanism of strain-induced grain boundary migration and the discontinuous coarsening reaction is proposed for the formation of PFZs. Furthermore, PFZs were considered to be potential crack sources during the creep rupture test, leading to earlier failure of the material.