Hydrogen-bridged, cholesteric liquid-crystal (CLC) polymer networks are adopted as an optical sensor material to distinguish between ethanol and methanol. Fast uptake of the alcohols is facilitated by an incorporated porosity created by breaking the hydrogen bridges and by a previously removed non-reactive liquid-crystal agent. The discrimination between the alcohols is based on the diversity in molecular affinity of ethanol and methanol with the hydrogen-bridged CLC polymer networks. The CLC networks are molecular-helix-based, one-dimensional bandgap materials with a discrete reflection band in the visible part of the spectrum that depends on the pitch of the molecular helix. The changes in positions of the reflection bands of the CLC network accurately discriminate between the alcohol types and provide information on their ratio in case they are blended.