Aromatic　sulfur-containing　compounds　are　main　constraints　for　liquid　hydrocarbon　fuels　upgrading　furtherly.　Efficient　adsorption　of　the　sulfur-containing　compounds　by　metal–organic　frameworks　(MOFs)　is　still　a　challenging　because　of　single　and　inert　adsorptive　sites.　We　herein　represent　a　new　strategy,　constructing　dinuclear-crossed　secondary　building　units　(SBUs)　in　MOFs,　for　generating　Cu(I)　and　Cu-coordination-unsaturated　sites　(Cu-CUS).　The　high-performance　Cu(I)　and　Cu-CUS　sites　are　controllable　by　modulating　the　organic　ligands　molar　ratio　of　1,3,5-benzenetricarboxylic　acid　/　4-pyrazolecarboxylic　acid　(BTC/PyC).　The　optimal　Cu-BTC/PyC-1/1　with　abundant　Cu(I),　Cu-CUS,　and　large　surface　areas　thus　exhibits　dibenzothiophene　adsorption　capacity　of　51.11　mg　S/g.　The　result　shows　100.3%　and　47.8%　increased　adsorption　capacity　comparison　with　that　of　sole　Cu-PyC　(25.52　mg　S/g)　and　Cu-BTC　(34.57　mg　S/g)　respectively.　The　high　adsorption　capacity　originates　from　electron-transfer　mechanism　between　empty-electron-orbital　Cu(I)/Cu-CUS　and　electron-enriched　aromatic　sulfur-containing　compounds.　The　molecular　engineering　for　building　multiple　adsorptive　sites　by　dinuclear-crossed　SBUs　strategy　exhibits　great　promising　for　MOFs-based　adsorbents　design.　©　2023　Elsevier　B.V.