Novel electronic states resulting from entangled spin and orbital degrees of freedom are hallmarks of strongly correlated f-electron systems. A spectacular example is the so-called hidden-order phase transition in the heavy-electron metal URu2Si2, which is characterized by the huge amount of entropy lost at T_{HO}=17.5K. However, no evidence of magnetic/structural phase transition has been found below T_{HO} so far. The origin of the hidden-order phase transition has been a long-standing mystery in condensed matter physics. Here, based on a first-principles theoretical approach, we examine the complete set of multipole correlations allowed in this material. The results uncover that the hidden-order parameter is a rank-5 multipole (dotriacontapole) order with nematic E^- symmetry, which exhibits staggered pseudospin moments along the [110] direction. This naturally provides comprehensive explanations of all key features in the hidden-order phase including anisotropic magnetic excitations, nearly degenerate antiferromagnetic-ordered state, and spontaneous rotational-symmetry breaking.