An alternating copolymer, poly(2,5-dioctyloxy-1,4-phenylene-alt-2,5-thienylene), has been synthesized and used in this research. The behavior of the floating film at the air-water interface has been investigated by measuring surface pressure versus area Langmuir isotherms and contemporaneously by reflection spectroscopy and Brewster angle microscopy. The floating films were transferred by the Langmuir-Schafer (horizontal lifting) method onto various substrates. It is apparent from these analyses that the effective conjugation length is larger than those in other electroactive polymers and that a strong coplanarity and interchain association takes place above all in the floating film on the water surface and in the transferred multilayers. Such films were used as the active layers in resistive chemical gas sensor devices, thus revealing excellent sensitivity toward NO2, reversibility, and time stability of the response.