A graphene/Fe loaded polyester fabric-PET with high electrical and catalytic properties has been successfully developed for the first time, via simple coating-incorporation method using hyperbranched poly(amidoamine)-PAMAM dendrimer as binder. Both graphene oxide (GO/rGO) and zerovalent iron (Fe⁰) nanoparticles were loaded on polyester fabric surface before and after chemical grafting of PAMAM.  Full characterization of fabrics before and after modifications has been studied through sessile droplet goniometry, ζ–potential, K/S coating evenness, SEM, XPS, FTIR, TGA and DSC analysis. Results showed successful and uniform coating of GO/rGO and loading of Fe⁰ on PET; also allowed correlating the type of chemical moiety responsible for uniform GO coating, high Fe⁰ loading and their electrical and catalytic activities. Sheet resistance (R_sh) analysis was carried out to measure the conductivity of the samples. The lowest R_sh (corresponds to high conductivity) has been found in PET-PAM-rGO-Fe⁰ (0.74±0.13 kΩ/sq) followed by PET-rGO-Fe⁰ (1.32±0.18 kΩ/sq), PET-PAM-rGO (2.96±0.08 kΩ/sq) and PET-rGO (3.41±0.34 kΩ/sq). Furthermore, Fe⁰ –loaded samples were found to be effective in catalytic removal of toxic water pollutants (crystal violet dye) with ~99% removal of pollutants in around one hour, as observed by UV-vis spectroscopy. Relatively high electrical and catalytic activity in PET-PAM-rGO-Fe⁰ is related to the role played by PAMAM in uniform rGO coating and high Fe⁰ loading. These findings are of great importance as they allow envisaging the development of multifunctional textiles for combined smart and green chemistry application.