New carbonyl-functionalized quaterthiophenes, 5,5‴-diperfluorophenylcarbonyl-2,2′:5′,2″:5″,2‴-quaterthiophene [DFCO-4T], 5,5‴-diphenyl-2,2′:5′,2″:5″,2‴-quaterthiophene [DPCO-4T], and a polymer having the same basic motif as DFCO-4T, poly{1,4-bis[(3′-n-octyl-2,2′-dithiophene)carbonyl]-2,3,5,6-tetrafluorobenzene} [P(COFCO-4T)], have been synthesized, characterized, and the crystal structures of the molecules determined. Field-effect transistors fabricated with vapor-deposited and solution-cast films of DFCO-4T exhibit very high Ion:Ioff current ratios (up to 108) and electron mobilities up to ∼0.51 and ∼0.25 cm2·V-1·s-1, respectively. Solution-cast blends of P(COFCO-4T) and DFCO-4T (1:1 weight ratio) exhibit an electron mobility of ∼0.01 cm2·V-1·s-1 (Ion:Ioff = 104). Copyright © 2005 American Chemical Society.