Optical gain properties of blue emission oligomer 7‐unit 9,9‐dihexylfluorene (7F6) and its blends with polystyrene (PS) are reported. 7F6 demonstrates high photoluminescence quantum yield (65%), low amplified spontaneous emission threshold (EthASE = 0.6 kW cm−2), high gain coefficient (g = 90.9 cm−1), and extremely low distributed feedback laser threshold (Ethlaser = 86 W cm−2). Unlike polymer gain materials, the phase separation between 7F6 and PS is small even in a high blending ratio. The 70 and 50 wt% 7F6/PS blends display excellent gain properties with g = 70.7 and 64.3 cm−1, EthASE = 1.1 and 2.1 kW cm−2, and Ethlaser = 0.3 and 0.41 kW cm−2, respectively. The photostability and thermal stability are improved significantly by blending 7F6 into PS. These results promise 7F6/PS blends as a potential core material for expanding the bandwidth of plastic optical fiber.