An attempt has been made in the present work to investigate the role of anion for the uptake of Am(III)/Eu(III)/U(VI) by extraction chromatography (EXC) resin incorporating tetra-n-octyl-3-oxapentanediamide, commonly referred to as tetra-octyl diglycolamide (TODGA). In contrast to the nitric acid, perchloric acid medium favors extraction of trivalent metal ions even at low acidity (pH 2) and is almost insensitive to the acidity up to 5 M. Exceptionally large distribution coefficients (10⁵–10⁶) in the wide range of perchlorate concentration (10⁻²–5 M) is quite unusual and is by far the largest reported in the literature for Am(III)/Eu(III). Thermodynamic data suggests the possibility of inner sphere/cation exchange mechanism involving TODGA aggregates at higher acidity but outer sphere/cation exchange mechanism at low acidity for Eu(III). There is a possibility of employing TODGA based EXC resin for the remediation of liquid waste (contaminated with long lived transuranics like ^241/243Am and ²⁴⁵Cm) in the wide range of acidity.