An optical calcium sensor is fabricated based on a cholesteric liquid crystalline (CLC) polymer containing benzoic acid metal binding sites. A chiral imprinted CLC polymer is made which is subsequently treated with KOH to yield a responsive green reflecting film. On investigation of various metal ions, the polymer film shows a high optical response, and selectivity for calcium ions, which is related to the preorganized binding sites in the ordered liquid crystalline phase, leading to a blue reflecting film. The photonic polymer film is sensitive to Ca2+ within the physiologically relevant concentration range of 10-4 to 10-2 m. Measurement of total calcium concentration in serum is also investigated using the film. The optical responses of normal serum and samples mimicking hypocalcemia and hypercalcemia can be clearly distinguished, providing a cheap, battery-free, and easy-to-use alternative for calcium determination in clinical diagnostics.