In this work, a fluorinated pyrene-based organic semiconductor (L-F) has been designed and synthesized starting from a low-cost pyrene core functionalized with triphenilamine substituents at 1,3,6,8 positions (L-H), obtained via Suzuki coupling reactions. Its performance when used as green emitter in organic light emitting diodes (OLEDs) or as dopant-free hole-transporting material (HTM) in halide perovskite solar cells (PSCs) is higher than that of the L-H counterpart, in spite of its lower bulk hole-mobility (7.0 × 10−6 cm2/V) to L-H (1.9 × 10−4 cm2/V). In fact, the OLED devices based on a L-F active layer showed excellent green emission (brightness and current efficiency were 1759.8 cd/m2 and 3.7 cd/A, respectively) at a 4.5 V turn-on voltage. When the molecules were employed as a dopant-free HTM in PSCs, L-F led to a power conversion efficiency (PCE) and open circuit voltage (Voc) of 5.9% and 1.07 V, respectively, thus outperforming those of corresponding devices based on L-H (PCE = 5.0% and Voc = 0.87 V) under similar experimental conditions (AM 1.5G and 100 mW cm2). We attribute the enhancements of L-F-based optoelectronic devices (OLEDs and PSCs) to the observed better quality of the L-F films. The promising performance of L-F indicates that fluorination of small molecules can be an effective strategy to achieve low-cost and high-performing materials for energy harvesting and display-based organic electronic devices.