Cobalt　spinel　oxide　(Co3O4)　is　a　promising　nonprecious　catalyst　for　methane　combustion,　and　improving　its　catalytic　performance　through　structural　modulation　is　desirable.　Herein,　layer-structured　Cu2+-Co2+-Co3+　hydrotalcite-like　compounds　(HTlcs)　were　synthesized　via　methanol-assisted　oxidative　intercalation　and　used　as　a　single-source　precursor　to　prepare　copper-cobalt　spinels　for　the　first　time.　Their　characterizations　reveal　that　single-phase　and　composition-tunable　Cu2+-Co2+-Co3+　HTlcs　are　quantitatively　formed.　Upon　calcination,　Cu–Co　HTlcs　are　decomposed　into　CuxCo3–xO4　spinels　with　a　copper　content　of　up　to　10　at.%.　X-ray　photoelectron　spectroscopy　and　X-ray　absorption　spectroscopy　indicate　that　copper　ions　are　incorporated　into　the　Co3O4　lattice　as　tetrahedrally　coordinated　Cu+/Cu2+　and　octahedrally　coordinated　Cu2+.　The　presence　of　abundant　Cu+　suggests　a　redox　cycle　between　Co3+/Co2+　and　Cu2+/Cu+　couples,　highlighting　a　strong　electronic　interaction　between　copper　and　cobalt　species.　The　strong　Cu-O-Co　interaction　not　only　increases　oxygen　vacancies　and　surface　lattice　oxygen　mobility　by　weakening　the　Co–O　coordination　but　also　drastically　enhances　cobalt　reducibility.　Copper–cobalt　spinels　exhibit　noticeably　improved　catalytic　activity,　and　the　highest　activity　is　observed　for　Cu10-Co3O4,　facilitating　nearly　complete　CH4　conversion　at　500　℃　under　a　space　velocity　of　36,000　mL　gcat−1h−1.　This　catalyst　also　manifests　good　cycle　stability,　long-term　stability,　and　resistance　to　water　vapor.　The　synergetic　effect　between　Co3+/Co2+　and　Cu2+/Cu+　redox　couples　plays　a　key　role　in　improving　catalytic　activity.　The　proposed　HTlc　strategy　may　provide　a　new　opportunity　for　the　controlled　preparation　of　various　bi-metallic　and　multimetallic　cobaltite　spinels　for　different　applications.　©　2025