The organotin-polymer [(Me3Sn)4Fe(CN)6], 1, has been synthesized and characterized to test its potential application as catalyst. The structure of 1 consists mainly, of [Fe(CN)6]4− building blocks connected by the Me3Sn cations forming 3D-polymeric network. The iron (II) sites acquire distorted octahedral geometry while the tin atom exhibits TBPY-5 configured [Me3Sn(CN…)2] fragments. Fenton and photo-Fenton oxidative discoloration of methylene blue (MB) has been investigated by hydrogen peroxide catalyzed with the metal–organic framework, (MOF) 1. The reaction is first order with respect to MB dye. The irradiation of the reaction with UV-light enhanced the rate of MB mineralization. Mineralization of MB was investigated by FT-IR spectra. Disodium salt of terephthalic acid photoluminescence probing technology was carried out to identify the reactive oxygen species. The different parameters that affect MB degradation rate were evaluated. Moreover, the efficiency of recycled the catalyst 1 and the mechanism of degradation of MB dye were investigated.