A series of one-armed cholesterol-linked azobenzene molecules named CholXAzo with different spacers were synthesized, in which Chol6Azo was found to have induced blue phases (BPs) with a concentration of 4.0 wt%. Under irradiation of 385 nm UV light with a density of 15.0 mW cm-2, photo-responsive behaviour of the 4.0 wt% Chol6Azo doped sample named B3 shows a sensitive temperature dependence, which means that at 38.0 °C a phase transition from BPs to the isotropic phase is induced; however, at 33.0 °C, this phase transition does not take place. Results from the research show that the optically binary phase transition behaviour of B3 is sensitive to the isomerization degree of Chol6Azo, which is closely related to the stability of the BP structure and there is a critical isomerization degree of 13.7% for the phase transition of the B3 liquid crystals. Further POM observation shows that the liquid crystal samples doped with different concentrations of Chol6Azo have an increasing transition temperature for photo-induced phase transition from the BP to the isotropic phase along with the increasing concentration of Chol6Azo, which are found to have the same changing tendency with phase transition temperature from the isotropic phase to BPs and a phase diagram is made to map the optically binary behaviour of Chol6Azo doped blue phase liquid crystals. At last, a simple pattern with the BP and the isotropic phase arranged at an interval was made in this optically binary liquid crystalline blue phase under a suitable photomask.