Ladder-type π-conjugated compounds containing a benzo[2,1-b:3,4-b′]difuran skeleton, such as dibenzo[d,d′]benzo[2,1-b:3,4-b′]difuran (syn-DBBDF) and dinaphtho[2,3-d:2′,3′-d′]benzo[2,1-b:3,4-b′]difuran (syn-DNBDF) were synthesized. Their photophysical and electrochemical properties were revealed by UV-vis absorption and photoluminescence spectroscopy and cyclic voltammetry. Organic field-effect transistors (OFETs) were fabricated with these compounds as organic semiconductors, and their semiconducting properties were evaluated. OFETs with syn-DBBDF and syn-DNBDF showed typical p-type characteristics with hole mobilities of &lt
1.5 × 10-3 cm2·V-1·s-1 and &lt
1.0 × 10-1 cm2·V-1·s-1, respectively.