Calix[4]pyrroles have been studied extensively as effective receptors for anions, ion-pairs and transmembrane anion transporter in recent years. A ‘Picket Calix[4] pyrrole’ represents a calix[4]pyrrole bearing aryl groups at diametrical meso-positions in cis-fashion when it becomes a cone conformation. We have investigated anion recognition properties of these classes of hosts using fluorescence dye displacement assay technique. Due to conformationally flexible nature and low energy barrier between different conformers, calix[4]pyrroles adopt many different conformations depending on the solvents and the meso-substituents. In the case of the meso-aryl picket calix[4]pyrrole, the anion usually occupies the deep pocket created by the two, axially positioned meso-aryl groups. In order to clarify the binding modes of the meso-picket calix[4]pyrroles upon anion binding, a meso-ethynyl extended aryl-picket calix[4]pyrrole is designed and synthesized by directly anchoring phenylethynyl groups at diametrically opposed meso-positions. Single crystal X-ray crystallographic analysis of the host-chloride complex revealed an unusual pseudo-equatorial conformation of the bulky meso-phenylethynyl groups other than pseudo-axial conformation which is corroborated by solution state anion binding studies. Comparative anion binding properties and structure-property relationship for the ethynyl extended receptor and analogous systems will be presented in details.