We describe the synthesis of four water-soluble aryl-extended calixpyrrole receptors and report their binding properties with multiple neutral polar guests in water. The prepared receptors present different functionalization at their upper rims and have in common the placement of water solubilizing pyridinium groups at their lower rims. We investigate the interaction of the receptors with a guest series in water solution using 1H NMR titrations and ITC experiments. Despite the known competitive nature of water for hydrogen-bonding interactions, we demonstrate the formation of thermodynamically highly stable 1 : 1 inclusion complexes stabilized by hydrogen-bonding interactions. We show that increasing the hydrogen-bond acceptor character of the guest has a positive impact on binding affinity. This result suggests that the receptor’s cavity is indeed a better hydrogen-bond donor to interact with the guests than water molecules. We also assess the important contribution of the hydrophobic effect to binding by comparing the binding affinities of analogous inclusion complexes in water and chloroform solutions. The more polar guests are bound with similar affinities in the two solvents. We compare the binding properties of the different complexes in order to derive general trends.