The use of terephthalate ligands with CnH2n+1NH-chains (n ≥ 6) led to the isolation of the first examples of Zr4+-terephthalate MOFs with 6-connected frameworks. The material with hexyl-amino functional groups has been proved to be an exceptional sorbent for the removal of As(III/V) toxic species from aqueous media, whereas MOFs with heptyl to dodecyl-amino moieties are superhydrophobic with promising oil-water separation properties.