Full-liquid evaporator is an important part of the Organic Rankine Cycle (ORC). It is of great guiding significance to study the pool boiling heat transfer characteristics (high-temperature level) of the evaporator heat exchange tube for evaporator design. The pool boiling heat transfer characteristics (high-temperature level) of working fluid R245fa outside smooth tube and fish-scale tube are analyzed. The outcomes exhibit that the overall Heat Transfer Coefficient (HTC) of the smooth tube is 1.9–3.9 kW m−2 K−1, and the fish-scale tube is 3.8–4.3 kW m−2 K−1 when the saturation temperature of organic working medium R245fa is 80.5 °C. The HTC outside the fish scale tube is 1.45–3.13 instances that of the smooth tube. The external HTC of the smooth tube and fish-scale tube increases with the increase of heat flux, but the strengthening rate decreases. After the outer wall of the heat exchange tube used in the ORC evaporator is strengthened, the water velocity in the tube increases, which can not only strengthen the heat exchange in the tube but also play an anti-scaling effect.