A set of glutaraldehyde (GA) cross-linked poly(vinyl alcohol)/activated carbon (PVA/GA/AC) composites prepared in the form of monolithic rods using a cryogelation technique and studied using adsorption, mercury porosimetry, scanning electron microscopy (SEM), and quantum chemistry methods display porosity similar to that of PVA/GA cryogel at a high GA content (content ratio GA/AC = 1 and GA/PVA = 0.2). GA cross-linked PVA multilayer coverage is an effective barrier for adsorption on AC particles. Variations in surface chemistry (AC initial and oxidized in air at 300 掳C for 12 h) and content (14鈥?2.5%w/w) of ACs in PVA/GA/AC composites relatively weakly affect their textural characteristics at a high GA content (specific surface area SBET < 120 mp>2p>/g, pore volume Vp < 0.35 cmp>3p>/g). However, PVA/GA/AC composite rods formed with a lower concentration of GA (content ratio GA/AC = 1/6 and GA/PVA = 1/10) have significantly greater SBET (500 mp>2p>/g) and Vp (>0.55 cmp>3p>/g) values because of improved accessibility of the AC surface. This provides better adsorption of methylene blue as a probe compound.