The　effective　improvements　in　structure　and　composition　are　critical　to　the　performances　of　inexpensive　elec-trocatalysts　based　on　transition　metal　chalcogenides　(TMCs),　especially　in　dye-sensitized　solar　cell　(DSSC)　and　hydrogen　evolution　reaction　(HER),　which　will　be　an　ongoing　challenge.　Herein,　a　novel　method　of　forming　Ni-Fe-Mo　sulfide　composite　electrocatalyst　(denoted　as　Ni-Fe-MoSx)　by　adding　molybdenum　element　when　modi-fying　the　active　sites　on　the　surface　of　Ni-Fe　layered　double　hydroxide　(Ni-Fe　LDH)　was　proposed　and　studied.　Beginning　with　MIL-88A　(Fe),　Ni-Fe　LDH　was　prepared　by　the　hydrolysis　of　nickel　and　iron　ions　in　alkaline　solution,　and　then　vulcanized　by　ammonium　tetrathiomolybdate　to　synthesize　Ni-Fe-MoSx　electrocatalyst　with　hollow　bipyramidal　structure　and　rich　active　sites　on　the　modified　surface.　Benefiting　from　the　advantages　of　hollow　construction　and　the　enhanced　intrinsic　activity　of　more　active　sites,　Ni-Fe-MoSx　electrode　delivered　an　outstanding　power　conversion　efficiency　(PCE)　of　9.37%　in　DSSC.　Accompanying　with　a　low　onset　potential　of　30.4　mV,　its　stability　in　acid　HER　could　maintain　well　over　long　periods　of　time.　The　successful　implementation　of　the　scheme　is　expected　to　provide　a　novel　avenue　for　synthesizing　bifunctional　electrocatalysts　based　on　TMCs.