The aim of this work was to reduce/minimize Li in Li-LSX by replacing the 70% Li+ cations in Li-LSX that are bonded to the interior or inaccessible sites which are not used for adsorption. Thus, mixed-cation LiCa-LSX containing minimum lithium were prepared by exchanging small fractions of Li+ into Ca-LSX, followed by dehydration under mild conditions to avoid migration/equilibration of Li cations. Comparisons of adsorption isotherms of N-2/O-2 and heats of adsorption for the LiCa-LSX samples with that for pure-cation Li-LSX and Ca-LSX provided strong evidence that significant amounts of these Li cations indeed remained on the exposed sites (SIII). The mixed-cation LiCa-LSX samples were compared against the pure-cation Ca-LSX and Li-LSX based on their performance for oxygen production by PSA, via model simulation. The results showed that the mixed-cation LiCa-LSX samples yielded significantly higher O-2 product productivities at the same product purity and recovery than their pure-cation precursor (Ca-LSX). (c) 2017 American Institute of Chemical Engineers AIChE J, 64: 406-415, 2018