Vacuum deposition of linear rod-like pi-conjugated poly(arylene)s [poly(p-phenylene) PPP, poly(thiophene-2,5-diyl) PTh, and poly(2,2’-bipyridine-5,5’-diyl) PBpy] gives thin films of poly(arylene)s on various substrates. IR spectra of the films are essentially the same as those of original polymers. UV-visible and photoluminescence spectra of the films also show peaks near those observed with the original polymers. Vacuum deposited (vd-) PPP molecules stand upright on carbon and metal substrates as revealed by regular electron diffraction spots observed with the thin film of PPP. The degree of crystallinity of the PPP thin film depends on the kind of the substrate and increases in the order Au < Ag < Cu < Al < C, which is elucidated by the strength of interaction between PPP and the substrate. Similar orientation is observed with vd-PTh and -PBpy. In addition to the regular electron diffraction pattern, Debye-Scherrer rings are observable with the vd-PPP and -PTh films, and all the electron diffraction data are consistent with reported powder X-ray data of PPP and PTh. The vd-PPP and -PTh films are susceptible to p-doping with Epa of 1.34 and 0.71 vs Ag/Ag+, respectively, whereas the vd-PBpy film receives n-doping with Epc of -2.30 V vs Ag/Ag+. vd-PTh film forms an ohmic contact with Au, whereas Al/vd-PTh/Au and Al/vd-PTh/ITO devices show rectification of electric current with rectification ratios of 200 and 22, respectively. The rectification effect is accounted for by assuming an injection barrier between PTh and Al. Source-drain electric current of a field effect transistor using the vd-PTh film as an active layer can be controlled by gate bias.