Ascorbic acid plays an important role in the synthesis and metabolism of the human body. However, it cannot be synthesized by the human body and needs to be supplemented from exogenous food intake. Ascorbic acid is easily degraded during storage and heating, often causing its content in food to change. It is important to develop a sensitive and accurate photoelectrochemistry (PEC) biosensor for detecting ascorbic acid. The shortage of PEC materials with long illumination wavelengths and low bias voltages impedes the development of ascorbic acid biosensors. Herein, a 3,4,9,10-perylenetetracarboxylic dianhydride (PDA) self-assembly rod material was firstly reported to show significant photocurrent increases to ascorbic acid at 630 nm illumination and 0 V vs. Ag/AgCl. Moreover, the PDA self-assembly rod material was used as a PEC platform to detect ascorbic acid. This self-powered PEC biosensor exhibited a linear response for ascorbic acid from 5 μM·L−1 to 400 μM·L−1; the limit of detection was calculated to be 4.1 μM·L−1. Compared with other ascorbic acid biosensors, the proposed self-powered PEC biosensor shows a relatively wide linear range. In addition, the proposed self-powered PEC biosensor exhibits good practicability in beverage samples.