For the first time, the unusual ability of a Bi(III) immobilized on carboxyl‐terminated triazine dendrimer stabilized magnetic nanoparticles [Bi(III)‐CTTDS@Fe3O4] catalyst in the synthesis of indol‐3‐yl acrylates through the one‐pot four‐component reaction is reported. [Bi(III)‐CTTDS@Fe3O4] was characterized by Fourier transform infrared (FT‐IR), thermal gravimetrical analysis (TGA), elemental analysis (EA), field emission scanning electron microscopy (FE‐SEM), transmission electron microscopy (TEM), vibrating‐sample magnetometer (VSM), X‐ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP‐AES) techniques. Additionally, this catalyst can be conveniently separated from the reaction mixture and reused several times without significant loss of its activity.