The development of on-board sensors for emissions monitoring is necessary for continuous monitoring of the performance of catalytic systems in automobiles. We have fabricated mixed potential electrochemical gas sensing devices with Pt, La<
sub>
0.8<
/sub>
Sr<
sub>
0.2<
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CrO<
sub>
3<
/sub>
(LSCO), and Au/Pd alloy electrodes and a porous yttria-stabilized zirconia electrolyte. The three-electrode design takes advantage of the preferential selectivity of the Pt + Au/Pd and Pt + LSCO pairs towards different species of gases and has additional tunable selectivity achieved by applying a current bias to the latter pair. Voltages were recorded in single, binary, and ternary gas streams of NO, NO<
sub>
2<
/sub>
, C<
sub>
3<
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H<
sub>
8<
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, and CO. We have also trained artificial neural networks to examine the voltage output from sensors in biased and unbiased modes to both identify which single test gas or binary mixture of two test gases is present in a gas stream as well as extract concentration values. We were then able to identify single and binary mixtures of these gases with accuracy of at least 98%. For determining concentration, the peak in the error distribution for binary mixtures was 5% and 80% of test data fell under <
12% error. The sensor stability was also evaluated over the course of over 100 days and the ability to retrain ANNs with a small dataset was demonstrated.