The symmetrical planar star-shaped organic semiconductor DMM-TPA-[DTS(BTTh(3))](3) with fused TPA core donor and three branch motifs, DTS(BTTh(3)), exhibited efficient p-type semiconducting performance in solution-processed SMOSCs and OFETs compared to the tilted star-shaped TPA-[DTS(BTTh(3))](3); a noteworthy PCE value of 4.16% was observed, with a hole mobility and on/off ratio of 7.6 × 10(-3) cm(2) V(-1) s(-1) and 5 × 10(6), respectively.