Construction　bimetallic　transition　metal　selenides　with　complex　hollow　structures　is　of　significant　importance　but　also　extremely　challenging.　In　this　work,　starting　form　metal-organic　frameworks　(MOFs),　we　have　successfully　synthesized　the　unique　hierarchical　(Ni0.33Co0.67)Se2　complex　hollow　spheres　(CHSs),　which　manifest　high　specific　capacitance　as　well　as　excellent　rate　performance　and　cycling　stability,　making　them　promising　electrode　materials　for　pseudocapacitors.　The　hierarchical　(Ni0.33Co0.67)Se2　CHSs　display　a　high　specific　capacitance　of　827.9　F　g−1　at　the　current　density　of　1　A　g−1　and　can　still　retain　646.2　F　g−1　at　a　very　high　current　density　of　30　A　g−1.　Besides,　a　high　capacitance　of　865.8　F　g−1　is　obtained　after　cycling　at　6　A　g−1　for　2000　cycles,　indicating　good　cycling　stability.　The　excellent　electrochemical　performance　could　be　owing　to　their　high　electrical　conductivity　and　hierarchical　complex　hollow　structure.　Furthermore,　an　asymmetric　supercapacitor　(ASC)　device　employing　(Ni0.33Co0.67)Se2　CHSs　as　positive　electrode　and　activated　carbon　(AC)　as　negative　electrode　is　also　fabricated,　which　displays　a　high　energy　density　of　29.1　Wh　kg−1　at　a　power　density　of　800　W　kg−1.　These　electrochemical　results　indicate　the　hierarchical　(Ni0.33Co0.67)Se2　CHSs　could　be　promising　electrode　materials　for　pseudocapacitors.　The　present　work　might　also　contribute　to　the　rational　construction　of　metal　selenides　with　complex　hollow　structures　for　high-performance　energy　storage.　©　2018　Elsevier　Ltd