Abstract Reaction of resorcinol with phosphorylated acetals or ethoxyvinylphosphonic acid esters in acidic media leads to calix [4] resorcinarenes, containing dialkoxyphosphoryl fragments at the lower rim of the molecule. When the alkyl substituent in alkoxy groups at phosphorus atom is not very long, a partial hydrolysis of the initially formed products takes place to give calixarenes with alkoxyhydroxyphosphoryl fragments.