In this work, following the Discrete de Rham (DDR) paradigm, we develop an arbitrary-order discrete divdiv complex on general polyhedral meshes. The construction rests 1) on discrete spaces that are spanned by vectors of polynomials whose components are attached to mesh entities and 2) on discrete operators obtained mimicking integration by parts formulas. We provide an in-depth study of the algebraic properties of the local complex, showing that it is exact on mesh elements with trivial topology. The new DDR complex is used to design a numerical scheme for the approximation of biharmonic problems, for which we provide detailed stability and convergence analyses. Numerical experiments complete the theoretical results.