An optical pH sensitive membrane for optical pH sensors has been developed by covalently immobilizing phenol red on optical transparent cross-linked polyvinyl alcohol (PVA) membrane surfaces. The phenol red was first reacted with acrylamide to form a product of acrylamide grafted phenol red (AAGP), then the AAGP was covalently immobilized to the PVA membrane via surface grafting-polymerization using Fe^2+/H2O2 as initiator. The performance of the pH sensitive membrane was investigated and the results showed that the pH sensitive membrane has some features including a linear response scope from pH 6.5 to 8.5 closed with phenol solution, a rapid response time (〈:20 s), good reproducibility, reversibility, excellent stability and easiness of fabrication. These show that the pH sensitive membrane can be used as a sensitive layer for optical pH sensor.