A series of malonate derivatives-calix[4]arene conjugates were synthesized through Knoevenagel condensation reaction between formyl-tetrapropoxycalix[4]arene and malonate derivatives. The structures of the resulting malonate derivative functionalized calix[4]arenes were characterized by NMR spectroscopy, mass spectrometry and even single crystal X-ray diffraction analysis. A series of malonate derivatives-calix [4] arene conjugates were synthesized through Knoevenagel condensation reaction between formyl-tetrapropoxycalix [4] arene and malonate derivatives. The structures of the malonate derivative functionalized calix [4] arenes wereased by NMR spectroscopy, mass spectrometry and even single crystal X-ray diffraction analysis.