A paramagnetic A3B-type Mn(III)-porphyrin was synthesized and characterized by physical–chemical methods (UV-Vis, FT-IR, 1H-NMR spectroscopy). The obtained compound was tested as a sensitive material for the spectrophotometric and potentiometric detection of iodine species. Using UV-Vis spectroscopy, the triiodide anions could be detected with high precision in the concentration interval of 1.02 × 10−5 to 2.3 × 10−5 M, with an LOD of 9.44 × 10−6 M. The PVC-based electrode using DOP as a plasticizer showed a sensitivity toward iodide in a wide concentration range of 1.0 × 10−5 to 1.0 × 10−1 M, with an LOD of 8.0 × 10−6 M. Both methods are simple, low-cost, and efficient for the detection of iodine species in synthetic samples and pharmaceuticals.