An innovative nanocatalyst (KCC-1-nPr-Met) has been prepared from the covalent attachment of metformin on the channels and the pores of n-propyl amine functionalized dendritic fibrous nanosilica (DFNS) and used towards efficient, green, and high yield synthesis of tetrahydro-4H-chromenes derivatives by one-pot three-component reaction of aromatic aldehydes, malononitrile, and dimedone in H2O-EtOH at room temperature. The designed nanocatalyst has been characterized by energy dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FT-IR), and adsorption/desorption analysis (BET) techniques. Also, field emission scanning electron microscopy (FE-SEM) was used to study the morphology of prepared nanocatalyst. The engineered nanocatalyst with uniform fibrous spheres has dendritic structure, high pore volume (0.35 cm3/g), and great surface area (178 m2/g). Hence, the specific dendritic structure of the prepared nanocatalyst not only improve the diffusion ability of the reactants and products, but also, increase the availability of dynamic sites in the pores and channels of the catalyst. According to the obtained results, a unique strategy was proposed towards the synthesis of important biologically active scaffolds in the presence of nontoxic and environmental friendly nanocatalyst and media. Milder reaction conditions (room temperature), shorter reaction times (5-30 minutes), excellent yields (92%-98%) of the products with higher purity, very simple workup procedure, and using of EtOH: H2O as a green solvent are the advantages of the presented work.