The adsorption/desorption of N2 at 77 K and the adsorption from aqueous solution at 298 K of four organic probe molecules of different sizes (phenol, 4-nitrophenol, orange II, naphthol green B) were studied for a phthalocyanine network polymer of intrinsic microporosity (PIM) and for an activated carbon (Darco 20-40 mesh). N2 sorption analysis gave similar surface areas for the PIM and the carbon (610 and 545 m2 g(-1), respectively) but showed differences in pore size distribution, the PIM being essentially microporous (pore size < 2 nm), with a high proportion of ultramicropores (<0.7 nm), while the carbon had a broader pore size distribution, extending into the mesopore region. The carbon acted as an adsorbent for all the organic probe molecules studied, while the PIM was more selective, adsorbing the smaller molecules but rejecting the large dye naphthol green B. The PIM offers selectivity combined with a well-defined chemical structure incorporating catalytic sites.