Two isomeric pyrenodithiophenediones and their triisopropylsilyl(TIPS)-ethynyl-functionalized derivatives were synthesized and characterized. With treatment of excess lithium TIPS-acetylide, the isomeric diones could undergo Michael and carbonyl additions to form three derivatives with four, three, and two TIPS-ethynyl groups, respectively. The isomeric TIPS-ethynyl-functionalized derivatives show different physicochemical properties. The single-crystalline transistors based on TIPS-ethynyl-functionalized derivatives exhibit a promising p-type transport behavior, with hole mobilities up to 0.51 cm2 V-1 s-1.