Gallium(III) was extracted at pH 3.5 by equilibrating eight min with 10mL of 0.0001M acetyl derivative of calix(6)arene in xylene. Gallium(III) was stripped quantitatively with 0.1N hydrochloric acid and determined spectrophotometrically with 0.01% PAR at 510nm. The nature of the extracted species was determined from the log-log plots and its stoichiometry was confirmed by numerical treatment to experimental data. The IR analysis of Ga(III) loaded organic phase was also studied. The conformational change of reagent during complex formation was studied from the H-1 NMR treatment. The temperature dependence of the extraction equilibrium and metal loading capacity of the reagent was also evaluated. The proposed method was successfully applied for the extraction and separation of multicomponent mixtures, synthetic mixtures, and binary and ternary separation of gallium from the associated elements. The results obtained were reproducible and accurate.