Extraction of Eu, Am, Tc and Pd by 20 new phosphorylated calixarenes was investigated. In contrast to routine phosphine oxides, with decreasing the length of alkyl substituent at phosphorus atom in calix[4] arenes, the Eu and Am extraction maximum is shifted to more acidic region. Similar effect is observed in Tc and Pd extraction. All calixarenes effectively extract technetium from acidic (to 1 M HNO₃) media. There is practically no "cooperative effect": phosphorylated calix[4]arenes extracts technetium only two times better than monodentate analog. With decreasing the phosphoryl oxygen basicity the distribution coefficients of technetium and palladium decrease. The calixarene ring size, structure and length of bridge group and position of phosphoryl groups on upper or lower rims do not considerably affect technetium and palladium extraction. As to palladium extraction by phosphorylated calix[4]arenes, there is observed the moderate "cooperative effect" (around 10). As distinct from routine extractants, the phosphorylated calix[4] arenes afford the combined recovery of REE, TPE, technetium and palladium from acidic media.