Herein, we report the fabrication of UV-active NaNbO3/Al2O3 (30 wt.%) ferroelectric heterojunction photocatalyst with enhanced photoelectrochemical activity to Methylene Blue (MB). Pure NaNbO3 nanorods (NRs) were synthesized by a facile hydrothermal process and NaNbO3/Al2O3 composite was prepared by an ultrasonic vibration method. The heterostructures showed a remarkable increase in photocurrent density and the MB degradation ratio reached 88% in the initial 15 min and eventually reached 98.6% in 75 min. The high photocatalytic efficiency is attributed to the ferroelectric polarization of NaNbO3 with the forming of heterojunction electric fields assisted by Al2O3. These properties demonstrate that NaNbO3/Al2O3 ferroelectric heterojunction photocatalyst shows promising photoactivity and provides an effective method to improve the photocatalytic properties of other ferroelectrics.