The synthesis of structurally new types of ferrocene-based ureas, in which the ferrocene moiety is simultaneously attached to two urea groups, have been prepared directly from 1,1'-bis(isocyanato)ferrocene 1. Homoditopic receptors 2a-e show spectral and electrochemical anion-sensing action: they display a selective downfield shift of the urea protons and a cathodic shift of the ferrocene/ferrocinium redox couple with hydrogen phosphate and fluoride anions. In addition, receptor 2d based on an unprecedent tetraaza[9]ferrocenophane architecture, shows spectral, electrochemical, and selective fluorescent responses to fluoride anion.