AbstractWe used a simple technique to create palladium nanoparticles on diamine functionalised graphene (Pd(0)‐AAPTMS@G) with an average particle size of 5.5 nm. Our earlier research described the Pd(0)‐AAPTMS@G material as an effective catalyst with outstanding conversion and yields for the Suzuki coupling reaction. We reported the characterisation data for Pd(0)‐AAPTMS@G catalysts previously. Here, we provide a narrative for the excellent selectivity and high yields (92–100 %) for the Mizoroki–Heck coupling product over the same Pd(0)‐AAPTMS@G catalyst. Six uses of the generated catalyst are possible without any activity loss. We also compared the catalyst characterisation for both fresh and reused catalysts.