Electronic states of iron in the lower mantle's dominant mineral, (Mg,Fe,Al)(Fe,Al,Si)O3 bridgmanite, control physical properties of the mantle including density, elasticity, and electrical and thermal conductivity. However, the determination of electronic states of iron has been controversial, in part due to different interpretations of Mössbauer spectroscopy results used to identify spin state, valence state, and site occupancy of iron. We applied energy-domain Mössbauer spectroscopy to a set of four bridgmanite samples spanning a wide range of compositions: 10–50% Fe/total cations, 0–25% Al/total cations, 12–100% Fe3+/total Fe. Measurements performed in the diamond-anvil cell at pressures up to 76 GPa below and above the high to low spin transition in Fe3+ provide a Mössbauer reference library for bridgmanite and demonstrate the effects of pressure and composition on electronic states of iron. Results indicate that although the spin transition in Fe3+ in the bridgmanite B-site occurs as predicted, it does not strongly affect the observed quadrupole splitting of 1.4 mm/s, and only decreases center shift for this site to 0 mm/s at ~70 GPa. Thus center shift can easily distinguish Fe3+ from Fe2+ at high pressure, which exhibits two distinct Mössbauer sites with center shift ~1 mm/s and quadrupole splitting 2.4–3.1 and 3.9 mm/s at ~70 GPa. Correct quantification of Fe3+/total Fe in bridgmanite is required to constrain the effects of composition and redox states in experimental measurements of seismic properties of bridgmanite. In Fe-rich, mixed-valence bridgmanite at deep-mantle-relevant pressures, up to ~20% of the Fe may be a Fe2.5+ charge transfer component, which should enhance electrical and thermal conductivity in Fe-rich heterogeneities at the base of Earth's mantle.