The ability of capturing guest molecules in a selective way is one of desirable properties of modern structured adsorbents. This refers to a wide class of guest molecules, especially to those which are chiral and whose enantiomers are to be efficiently separated. In this contribution, using Monte Carlo modeling, we show how simple molecular building blocks with cruciform shape can be used to create 2D porous matrices with tunable adsorptive properties. To that end we consider different self-assembled structures comprising cross-shaped molecules and probe their ability to retain model guest molecules differing in size and shape. In particular we focus on the adsorption of enantiomeric pairs on these substrates and quantify the associated selectivity. The obtained results show that a suitable choice of the building block, including size and aspect ratio allows for the creation of 2D functional matrices with programmed adsorption performance. The findings of our theoretical investigations can be helpful in designing molecular guest-host systems with potential applications in separations, sensing and heterogeneous catalysis. (C) 2016 Elsevier B.V. All rights reserved.