The quantitative trace determination and separation from individual rare earths is a difficult task, with this view a new synthesized and functionalised Calix[4]resorcinarene polyhydroxamic acid is used for sorption, speciation, sequential separation and trace determination of La (II), Ce (III), Ce (IV), Nd (III) and Gd (III). The rare earths are quantitatively separated and trace determination in the range of 2–15 ng with the selectivity order La (III) > Ce (III) > Nd (III) > Gd (III). The column parameters like pH, flow rate and distribution were evaluated. The effect of various electrolytes and diverse metal ions in separation are studied. The present method is applied for estimation of rare earths in monazite and other geological specimens. Suitable eluents were used to effectuate the separations of the binary and ternary combinations.