Here, a pillar[5]arene derivative including biphenylcarboxylic acid groups was designed for obtaining a macrocycle with an ideal cavity for volatile organic compounds. The pillar[5]arene -biphenylcarboxylic acid (P5-BPCA) based Langmuir-Blodgett (LB) thin films were produced onto 50 nm thick gold-coated glass and 3.5 MHz quartz crystal substrates to form a thin film chemical sensor element. Surface plasmon resonance (SPR) and Quartz crystal microbalance (QCM) techniques were employed to characterize all the P5-BPCA LB thin film layers. The mass of LB film layer loaded onto a quartz crystal and the resonance frequency shifts per layer were determined to be 711.71 ng per layer (2.68 ng mm −2 ) and 48.24 Hz per layer, respectively. The P5-BPCA LB thin film sensor element was exposed to various haloalkane and aromatic hydrocarbon vapors. The sensitivities of the P5-BPCA LB film sensor were determined between 1.776 and 3.976 Hz ppm −1 . Sensitivity with detection limits were obtained between 0.754 and 1.689 ppm against organic vapors. The results showed that P5-BPCA LB thin film was highly selective with a large response to chloromethane vapor.