A new system for CO2 measurement (0-100%) by based on a paired emitter-detector diode arrangement as a colorimetric detection system is described. Two different configurations were tested: configuration 1 (an opposite side configuration) where a secondary inner-filter effect accounts for CO2 sensitivity. This configuration involves the absorption of the phosphorescence emitted from a CO2-insensitive luminophore by an acid-base indicator and configuration 2 wherein the membrane containing the luminophore is removed, simplifying the sensing membrane that now only contains the acid-base indicator. In addition, two different instrumental configurations have been studied, using a paired emitter-detector diode system, consisting of two LEDs wherein one is used as the light source (emitter) and the other is used in reverse bias mode as the light detector. The first configuration uses a green LED as emitter and a red LED as detector, whereas in the second case two identical red LEDs are used as emitter and detector. The system was characterised in terms of sensitivity, dynamic response, reproducibility, stability and temperature influence. We found that configuration 2 presented a better CO2 response in terms of sensitivity.