Hypothesis: Hybrid surfactants containing both alkyl and fluoroalkyl chains within the same molecule where modification of the azobenzene group will enable us to switch the superhydrophobic nature with an external light source, and the optical behavior will vary depending on the structure of the hydrophobic chains. Experiments: Surface activity and its optically-induced variation of the azobenzene-modified hybrid surfactants were characterized using the surface tensiometry, UV–vis and NMR spectroscopy and theoretical calculation. Findings: The hybrid surfactants are superhydrophobic in nature reducing the surface tension of water to near 20 mN/m. Photo-isomerization of the azobenzene group induces a drastic surface tension variation (Δγ), and particularly the compositions containing the octyl-fluorocarbon chain exhibit remarkable Δγ as much as 30 mN/m which is even higher than that of the conventional surfactants (Δγ ≈ 14–20 mN/m). Theoretical calculation suggests significantly higher hydrophilicity of the cis isomer, causing the drastic switch in the surface activity. These results indicate the promise of the hybrid surfactants as efficient surface/interface manipulators.