In the example when it says il pense à elle and it means he’s thinking of her. But in another example it says je parle de lui which means I speak of him. So de and à both mean of in these examples so I will as wondering when I would use à and when I would use de.
You can't by go the English translation if you want to decide whether to use de or à. There are some verbs that ask for de and others for à. You just have to learn the preposition along with the verb.
It also depends on what you want to say.
"Je lui parle" = I talk to him (or her)
"Je parle de lui" = I speak of him
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