A new study has been conducted to quantify lanthanide(III) ions using Arsenazo III–polyaminocarboxylic acid (PACA) system. The study disclosed two different analytically important information: (i) λmax of lanthanide–Arsenazo III complexes for lighter lanthanides like Ce(III) and Nd(III) did not shift from its original position on addition of PACA and (ii) for heavier lanthanides like Dy(III), Tm(III) and Lu(III) a new λmax at 538nm was observed, while wavelengths at 610nm and 654nm were disappeared in presence of ethylenediaminetertracetic acid (EDTA) and trans-1,2-Diaminocyclohexane-N,N,N′,N′-tetraacetic acid (DCTA), further the intensity of peak decreased with increase in lanthanide(III) ion concentration. Effect of ethylene glycol-bis(2-aminoethylether)-N,N,N′,N′-tetraacetic acid (EGTA) and N-(2-hydroxyethyl) ethylenediamine-N,N′,N′-triacetic acid (EDTA-OH) on Arsenzo(III)–Ln(III) complex is very weak and there is no analytically importance of such interaction. Moreover, this work confirms that Nd(III) and heavy lanthanides can be successfully determined with high accuracy in the working range of concentration of these metal ions.