Azobenzene photoresponsive materials have extensive prospects in applications of optical information storage, optical devices and so on. The technique of ionic self-assembly (ISA) is a new method developed recently to create supramolecular materials. The preparation methods of azobenzene photoresponsive materials and the theory of ISA technique are briefly introduced. The latest developments of azobenzene photoresponsive materials prepared by ISA technique are summarized into four kinds, including the ionic self-assembly of low molecular dye with surfactant, polyelectrolytes with azobenzene, highly branched macromolecules with azobenzene, and cyclodextrins with polyelectrolytes containing azobenzene. In addition, the progress tendencies of this technique are also introduced and prospected.

Contents
1 Introduction
2 The preparation methods of azobenzene photoresponsive materials and ultrathin films
2.1 Guest-Host
2.2 Covalent synthesis
2.3 Langmuir-Blodgett and monolayer films
2.4 Electrostatic layer-by-layer self-assembly
2.5 Non-covalent self-assembly
3 Ionic self-assembly
4 Application of ionic self-assembly in preparation of azobenzene photoresponsive materials
4.1 Ionic self-assembly of dye-surfactant complexes to prepare low molecular photoresponsive materials
4.2 Ionic self-assembly of polyelectrolytes-azobenzene to prepare supramolecular photoresponsive materials
4.3 Ionic self-assembly of highly-branched macromolecules with azobenzene
4.4 Ionic self-assembly of cyclodextrins with azobenzene polyelectrolytes to prepare orderly ultrathin films
5 Conclusions