She winked at him.

Literal

She [topic-は] him [to-に] eye-signal did.

目くばせ (めくばせ) is the noun for signaling with the eyes — winking, giving a meaningful look, exchanging glances with intent. The verb form 目くばせする takes the recipient with に. Note 目くばせ implies communication, often conspiratorial or coded, vs. the simpler ウィンク ('wink') as a single eye-shut gesture.