This work aims to discuss quantification of rare earth metals in a complex mixture using the novel multi-ionophore approach based on potentiometric sensor arrays. Three compounds previously tested as extracting agents in reprocessing of spent nuclear fuel were applied as ionophores in polyvinyl chloride (PVC)-plasticized membranes of potentiometric sensors. Seven types of sensors containing these ionophores were prepared and assembled into a sensor array. The multi-ionophore array performance was evaluated in the analysis of Ln3+ mixtures and compared to that of conventional monoionophore sensors. It was demonstrated that a multi-ionophore array can yield RMSEP (root mean-squared error of prediction) values not exceeding 0.15 logC for quantification of individual lanthanides in binary mixtures in a concentration range 5 to 3 pLn3+.