Understanding the competition between adsorption on confining interfaces and conformational behavior of polymers in confined volumes is a necessary condition for correct interpretation of chromatographic curves. Accordingly, we investigated the conformational behavior of linear (L) and star (S) polymers and the impact of the chain architecture on phase equilibria in porous media using Monte Carlo (MC) simulations. We focused on interaction chromatography (IC) under conditions close to the critical adsorption point (CAP). We evaluated the concentration-dependent partition coefficients by MC and used them as an input for the solution of a time-discretized mass balance equation which predicts the shapes of the elution curves. The study elucidates the effects of chain architecture on the IC separation mechanism and shows that IC is a promising method for the separation of L and S polymers.