The electronic spin state of Fe2+ in ferropericlase, (Mg0.75Fe0.25)O, transitions from a high-spin (spin unpaired) to low-spin (spin paired) state within the Earth’s mid-lower mantle region. To better understand the local electronic environment of high-spin Fe2+ ions in ferropericlase near the transition, we obtained synchrotron Mössbauer spectra (SMS) of (Mg0.75,Fe0.25)O in externally heated and laser-heated diamond anvil cells at relevant high pressures and temperatures. Results show that the quadrupole splitting (QS) of the dominant high-spin Fe2+ site decreases with increasing temperature at static high pressure. The QS values at constant pressure are fitted to a temperature-dependent Boltzmann distribution model, which permits estimation of the crystal-field splitting energy (Δ3) between the dxy and dxz or dzy orbitals of the t2g states in a distorted octahedral Fe2+ site. The derived Δ3 increases from approximately 36 meV at 1 GPa to 95 meV at 40 GPa, revealing that both high pressure and high temperature have significant effects on the 3d electronic shells of Fe2+ in ferropericlase. The SMS spectra collected from the laser-heated diamond cells within the time window of 146 ns also indicate that QS significantly decreases at very high temperatures. A larger splitting of the energy levels at high temperatures and pressures should broaden the spin crossover in ferropericlase because the degeneracy of energy levels is partially lifted. Our results provide information on the hyperfine parameters and crystal-field splitting energy of high-spin Fe2+ in ferropericlase at high pressures and temperatures, relevant to the electronic structure of iron in oxides in the deep lower mantle.