Does PSP have any teaching materials for learning English?

Yes, there is currently an English-Chinese dictionary in the homebrew software.

Among the PSP games, there is the Talkman series, which is a very good English learning textbook and has a Chinese version. If you have a PSP3000, you can even speak thanks to the built-in microphone, and the PSP can automatically recognize your spoken words and display them on the screen. The modes also include daily communication, travel English, etc. Learning English through videos and pictures is very entertaining and practical.