Complexes comprising a 4th‐generation dendrimer with 32 positively charged end‐groups and an oppositely charged linear polyelectrolyte along with explicit counterions are studied in an athermal solvent using MC simulations. The excluded volume between monomers, the full Coulomb potential between charges and the bending energy of the chain bonds are taken into account. The chain flexibility parameter is varied in a wide range, including the limiting cases of rigid and flexible chains. As the chains become more rigid, they take locally extended conformations within the complex. The conformations of the condensed chains are described in terms of loops, trains, and tails. In the limit of strong electrostatic coupling and high rigidity, long chains show a release of tails from the complex.
