Hypothesis: Switchable assemblies relevant for bio-applications may be accessed from water-soluble tetra-ortho-substituted azobenzenes that reversibly self-assemble and form complexes with β-cyclodextrin under visible light. Experiments: Two azobenzenes bearing either four fluorines or two chlorines and two fluorines in the ortho positions were synthesised with short poly(ethylene oxide) tails for water solubility. Photophysical properties were determined by UV–vis and 1H NMR spectroscopies, complexation with β-cyclodextrin was assessed by 1H NMR spectroscopy, and self-assembly in water was investigated by static and dynamic light scattering. Findings: Both molecules underwent trans–cis isomerization at 530 nm and cis–trans isomerization at 415 nm, with the cis forms exhibiting thermal half-lives > 300 days at room temperature. Both molecules formed inclusion complexes with β-cyclodextrin in water, with cis-4F-AZO-PEO binding 3-fold stronger than trans, and 2Cl2F-AZO-PEO binding significantly weaker. Self-assembly of pure 2Cl2F-AZO-PEO in water showed an open association process regardless of configuration, while 4F-AZO-PEO showed an open association process for cis (Nagg increasing from 30 to 1000) but a closed association process for trans (Nagg stable at ∼ 170). Aqueous solutions of 2Cl2F-AZO-PEO showed cloud points close to 45 °C, while the 4F-AZO-PEO isomers presented well-separated cloud points allowing reversible and all-visible transition between clear and turbid states at room temperature.