Abstract A new fluorinated manganese porphyrin, (Mn‐TPP‐ p ‐CF 3 ) is reported capable of providing, based on the Mn(III)/Mn(II) equilibrium, dual 1 H relaxivity and 19 F NMR response to redox changes. The physical‐chemical characterization of both redox states in DMSO‐ d 6 /H 2 O evidenced that the 1 H relaxometric and 19 F NMR properties are appropriate for differential redox MRI detection. The Mn(III)‐F distance (d Mn−F =9.7–10 Å), as assessed by DFT calculations, is well tailored to allow for adequate paramagnetic effect of Mn(III) on 19 F T 1 and T 2 relaxation times. Mn‐TPP‐ p ‐CF 3 has a reversible Mn(II)/Mn(III) redox potential of 0.574 V vs. NHE in deoxygenated aqueous HEPES/ THF solution. The reduction of Mn(III)‐TPP‐ p ‐CF 3 in the presence of ascorbic acid is slowly, but fully reversed in the presence of air oxygen, as monitored by UV‐Vis spectrometry and 19 F NMR. The broad 1 H and 19 F NMR signals of Mn(III)‐TPP‐ p ‐CF 3 disappear in the presence of 1 equivalent ascorbate replaced by a shifted and broadened 19 F NMR signal from Mn(II)‐TPP‐ p ‐CF 3 . Phantom 19 F MR images in DMSO show a MRI signal intensity decrease upon reduction of Mn(III)‐TPP‐ p ‐CF 3 , retrieved upon complete reoxidation in air within ~24 h. 1 H NMRD curves of the Mn(III)/(II)‐TPP‐ p ‐CF 3 chelates in mixed DMSO/water solvent have the typical shape of Mn(II)/Mn(III) porphyrins.