Polyethylene glycol‐(N‐methylimidazolium) hydroxide‐grafted hydroxyapatite encapsulated γ‐Fe2O3 nanoparticles, γ‐Fe2O3@HAp@PEG(mim)OH, were prepared and characterized by FTIR, SEM, TEM, TGA, and EDAX. This nanocomposite was applied as a novel, green, nanomagnetic, and recyclable basic phase‐transfer catalyst for the synthesis of tetrahydrobenzopyrans in high yields via the three‐component reaction of aromatic aldehydes, malononitrile, and dimedone or 1,3‐cyclohexanedione in aqueous media at ambient temperature.