Questions & Answers about Вечером мы собрались дома.
Вечером is the instrumental singular form of the noun вечер (“evening”).
In this sentence it functions as an adverbial expression of time, meaning “in the evening”.
Russian very often uses the instrumental case without a preposition to express “when?” with parts of the day and some time words:
- утром – in the morning (from утро)
- днём – in the daytime (from день)
- вечером – in the evening (from вечер)
- ночью – at night (from ночь)
So instead of saying в вечер (“in evening”), Russian just uses вечером. В вечер is not natural in modern standard Russian (it might appear only in poetry or very unusual style).