Colorimetric measurement is a versatile, low-cost method for bio-/chemical sensing and that has importance in biomedical applications. General carbon dioxide (CO₂) sensors based on colorimetric change of a pH indicator report only one parameter at a time and are cross-sensitive to relative humidity (RH). This work describes a novel optical fiber sensor with a thin film on the distal end of the fiber, combining colorimetric measurement and a white light Fabry–Pérot interferometer (FPI) for the simultaneous measurement of CO₂ and RH. The CO₂ sensitive dye ion-pair: thymol blue and tetramethylammonium hydroxide are encapsulated inside organically modified silica forming an extrinsic FPI cavity (refractive index of 1.501 ± 0.02 and thickness of 5.83 ± 0.09 μm). The sensor reversibly responds to 0–6% CO₂ and 0–90% RH with negligible cross-sensitivity and allows measurement of both parameters simultaneously. A sensitivity of ∼0.19 nm/%RH is obtained for RH measurement based on the wavelength shift of the FPI and there is a polynomial correlation between the average intensity of selected wavelengths and the concentration of CO₂. The applicability of the sensor is demonstrated by measuring the CO₂ and RH exhaled from human breath with a percent error of 3.1% and 2.2% respectively compared to a commercial datalogger. A simulation model is provided for the dye-encapsulated FPI sensor allowing simulation of spectra of sensors with different film thicknesses.