In this paper, a long-distance distributed pressure sensing system based on a special fiber and using frequency-scanned phase-sensitive optical time-domain reflectometry is proposed. The fiber shows high pressure sensitivity (159 MHz/bar) and low loss (3 dB/km) owing to its simple structure made of two large air holes in the cladding. The pressure response of the two orthogonal polarization axes of the fiber is explored distinctively. Distributed pressure sensing over a long sensing range (720 m) and high spatial resolution (5 cm) is demonstrated, resulting in 14,400 resolved sensing points with uncertainty on pressure of 0.49 bar. Discrimination between the temperature/strain and pressure responses is demonstrated, taking advantage of the different pressure and temperature sensitivities of the two polarization axes. In addition, the temperature response of the fiber is studied and the simulation results show the possibility of scaling the temperature sensitivity by adjusting the size of the core. The sensing distance limit due to crosstalk between the polarization axes is also discussed.