This work demonstrates the fabrication of chemical vapour sensors using Langmuir-Blodgett (LB) thin films, describing the thin film properties of a tetra-undecyl calixresorcinarene molecule along with a discussion of their sensing performance. Atomic Force Microscopy and Surface Plasma Resonance (SPR) methods were used for the characterization of the deposited thin films. As evidenced by these characterization methods, high quality and uniform Langmuir monolayers were formed on the water surface and can be transferred onto glass and gold-coated glass substrates with a transfer ratio of over 95%. The gas sensing properties towards the vapours of four volatile organic compounds were also examined by the SPR technique. Tetra-undecyl calixresorcinarene LB thin film is sensitive to organic vapours (benzene, chloroform, ethanol and toluene) with rapid response and recovery times, demonstrating promise towards future vapour detection applications, especially for the rapid detection of leaks or spillage.