The synthesis and catalytic application of a novel MgO containing periodic mesoporous organosilica with ionic liquid framework (MgO@PMO‐IL) is described. The prepared MgO@PMO‐IL was characterized by Fourier transform‐infrared spectroscopy, N2 adsorption/desorption, transmission electron microscopy, field emission‐scanning electron microscopy, thermogravimetric and inductively coupled plasma analyses. This nanocatalyst was successfully applied as a highly efficient and recoverable catalyst for the synthesis of novel spirooxindole‐furan derivatives via the three‐component reaction of 1,3‐dicarbonyl compounds, N‐phenacyl pyridinium salts and isatin derivatives. The products were achieved in high to excellent yields with a simple work‐up procedure and short reaction times, and the catalyst could be recovered through a simple filtration process and successfully reused seven times without any significant decrease in its efficiency.