〜と同時に
at the same time as, as soon as
Verb dictionary form / Noun + と同時に · い-adj + と同時に
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と同時に means "at the same moment as": ベルが鳴ると同時に、学生たちは教室を出た, "the moment the bell rang, the students left". It's more neutral and written than とたん, and it follows the dictionary form or a noun.
With nouns for life events, it means "as soon as": 卒業と同時に働き始めた, "I started work as soon as I graduated".
It also joins two roles or feelings that exist at once: 彼は歌手であると同時に、俳優でもある, "he's a singer and at the same time an actor"; うれしいと同時に不安だ, "I'm happy but also anxious".
Compare ながら, which is one person doing two actions side by side.
Examples
ベルが鳴ると同時に、学生たちは教室を出た。
The moment the bell rang, the students left the classroom.
卒業と同時に、東京で働き始めた。
As soon as I graduated, I started working in Tokyo.
彼は歌手であると同時に、俳優でもある。
He's a singer and, at the same time, an actor.
合格してうれしいと同時に、少し不安だ。
I'm happy I passed, but at the same time a little anxious.
ドアが開くと同時に、客が入ってきた。
Customers came in as soon as the doors opened.