A graphene/Fe loaded polyester fabric (PET) with robust electrical and catalytic properties has been successfully developed for the first time via a simple coating-incorporation method using hyperbranched poly(amidoamine) (PAMAM) dendrimer as the binder. Both graphene oxide (GO/rGO) and zerovalent iron (Fe0) nanoparticles were loaded on the polyester fabric surface before and after chemical grafting of PAMAM. Full characterization of fabrics before and after modifications has been performed by sessile droplet goniometry, ζ-potential, K/S coating evenness, SEM, XPS, FTIR, TGA and DSC analyses. The results showed successful and uniform coating of GO/rGO and loading of Fe0 on PET and also showed the correlation between the type of chemical moiety responsible for uniform GO coating, high Fe0 loading and their electrical and catalytic activities. Sheet resistance (Rsh) analysis was carried out to measure the conductivity of the samples. The lowest Rsh (corresponding to high conductivity) was found in PET-PAM-rGO-Fe0 (0.74 ± 0.13 kΩ sq-1) followed by PET-rGO-Fe0 (1.32 ± 0.18 kΩ sq-1), PET-PAM-rGO (2.96 ± 0.08 kΩ sq-1) and PET-rGO (3.41 ± 0.34 kΩ sq-1). Furthermore, Fe0-loaded samples were found to be effective in the catalytic removal of toxic water pollutants (crystal violet dye) with ∼99% removal of pollutants in around one hour, as observed by UV-vis spectroscopy. The relatively high electrical conductivity and catalytic activity of PET-PAM-rGO-Fe0 are related to the role played by PAMAM in the 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.