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Electron and spin dynamics of strongly correlated NdNiO3 are investigated across the metal–insulator transition with ultrafast optical spectroscopy at different temperatures, pump laser fluences, and laser polarizations. Transient differential reflectivity measurements on the insulating phase NdNiO3 show two characteristic electronic decay processes. The slow decay process, strongly dependent on coherent phonon excitation, is attributed to the electron–phonon interaction, while the fast decay process, to the electron-spin interaction. The temporal evolution of Kerr rotation reveals that net spin polarization can be induced by circularly polarized light in insulating NdNiO3 via electron excitation from the Ni t to e orbital, and two net spin polarizations with opposite directions are observed given the antiferromagnetic ordering in insulating NdNiO3. At the insulator-to-metal transition, the transient differential reflectivity reverses its sign; the metallic phase NdNiO3 also shows two characteristic electronic decay processes, a typical metallic decay processes and a slow decay process; the slow decay process is attributed to the interaction between electrons and the low frequency coherent phonons (2.45 THz). Our experiments demonstrate that the phase transition involves several processes upon continuous heating: the electron-spin interaction disappears at 9 K below the transition temperature; at the transition temperature, NdNiO3 transitions into the metallic phase and the antiferromagnetic ordering transitions into the paramagnetic ordering; at the transition temperature, the structure of NdNiO3 changes from a monoclinic structure () to a high temperature orthorhombic () structure. Such a structure change results in the change in phonon vibrations, and subsequently, leads to the disappearance of the electron–phonon interactions due to the insulating phase NdNiO3 and the emergence of other types of electron–phonon interactions due to the metallic phase. [ABSTRACT FROM AUTHOR]