tert-Octylcalix(8)arene and derivatives in which the lower rim hydroxy groups have been converted into OCH(2)CO(2)Et and OCH2COCH3 groups have been shown to form Langmuir-Blodgett films readily. These films adsorb a range of anions and cations from solution. XPS determinations on the films identify both the nucleus and the extent of adsorption into the films. For anions the order of selection is I > F > Br > Cl and for cations is Cs > Rb > Na much greater than K. Such films clearly have potential applications in ion sensing.