A series of π-conjugated 3,10-dialkyl-dinaphtho[1,2-b:2′,1′-d]chalcogenophenes incorporating S, Se, and Te as the central chalcogen atom was newly synthesized, and their optoelectronic and charge-transport properties were systematically investigated. High carrier mobilities of up to 4.7 cm² V⁻¹ s⁻¹ were achieved for solution-processed organic field-effect transistors using these materials as p-channel organic semiconductors.