Highly　efficient　capture　of　volatile　organic　compounds　(VOCs)　under　humid　conditions　is　a　significant　yet　formidable　task　for　metal-organic　frameworks　(MOFs).　Based　on　the　material　simulation　technique,　we　proposed　implanting　a　significantly　positive-density　ligand　(DABA)　to　modify　MIL-101　and　constructing　dual　positivecharging　centers　to　improve　MIL-101　competitive　adsorption　of　benzene　VOCs　over　H2O　vapors　both　thermodynamically　and　kinetically.　The　introduction　of　DABA　containing　two　-NH2　groups　with　electrostatically　positive　charges　into　MIL-101　resulted　in　the　formation　of　an　open　tetrahedral　cage　with　a　dual　positive　charging　center.　This　facilitated　strong　N-H...pi　interactions　with　toluene　molecules,　leading　them　to　accumulate　firmly　in　MOF　pores,　and　thus　dramatically　enhanced　its　adsorption　capacity　from　17　to　31　toluene　molecules　per　unit　cell　compared　to　pristine　MIL-101.　Moreover,　the　open　tetrahedral　cage　in　D-MIL-101　preferentially　captured　toluene　and　occupied　the　strongest　adsorption　sites　first,　thus　effectively　preventing　H2O　entry　into　MOF　pores　to　contact　with　hydrophilic　metal　sites.　This　realized　high　water　resistance　and　toluene　adsorption　uptake　under　high　humidity　conditions.　Results　showed　that　D-MIL-101　had　a　high　specific　surface　area　of　2558　m2/g　and　a　new　microporous　structure　of　9.5　angstrom　size.　It　presented　higher　toluene　uptake　of　4.69　mmol/g　at　lower　vapor　pressure　of　P/P0　=　0.013　and　298　K　temperature,　as　well　as　3.3　folds　higher　working　capacity　of　toluene　compared　to　pristine　MIL-101　under　80　%　RH.　This　study　presents　a　novel　approach　for　constructing　hydrophobic　MOFs　using　new　positive　charging　ligands　and　delves　deeper　into　the　competitive　adsorption　of　VOCs/H2O　in　MOF　composites　for　large-scale　applications.