The　adsorption　and　dissociation　of　molecular　oxygen　on　spinel　CuCr2O4　(100)　surface　were　carried　out　by　first-principles　calculations　based　on　density　functional　theory　(DFT).　The　calculated　results　indicate　that　the　Cr　site　is　most　favorable　for　atomic　oxygen　adsorption,　with　an　adsorption　energy　of　402.8　kJ/mol.　For　molecular　oxygen　adsorption,　there　are　three　types　of　favorable　interaction　modes:　O2　forms　bonds　with　the　Cu　site　or　O2　binds　to　two　Cr　sites　or　O2　interacts　with　both　Cu　and　Cr　sites　simultaneously.　The　lowest　activation　energy　(Ea　=　35.4　kJ/mol)　was　found　through　exploring　possible　reaction　pathways　for　O2　dissociation.　The　relationship　between　Ea　and　reaction　enthalpy　(ΔH)　for　O2　dissociation　adsorption　reactions　fits　Brønsted-Evans-Polanyi　(BEP)　behavior.　©　2008　Elsevier　B.V.　All　rights　reserved.