“She's been out of work for over a year now.”

Your friend got laid off last year and hasn't been able to find a new job. You're talking with another friend who knows her. You say this about how worried you both are.

She's been out of work for over a year now.

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be out of work

To be "out of work" means to not have a job, but it's specifically used for people who want to have a job but can't find one. You wouldn't use this phrase to describe a teenager with no job, or a stay-at-home mom, or a retired person. A more general way to describe anyone who doesn't have a job is to say they "are unemployed".

(someone) has been (adjective) for (some time)

This is used to describe a continued situation that started some time in the past and is still happening now:

She's been depressed for a few weeks.

The word that follows "been" should be an adjective or some longer phrase that works like an adjective. "Out of work" is a phrase that can be used like an adjective:

A lot of out-of-work actresses applied for the waitress job.

for (some length of time) now

Adding "now" to the end of a length of time shows that you think that it's a long time. If you just say how long something has been happening for, it's not clear how you feel:

We've been driving for five hours.

By adding now, you make it clear that you think the length of time is long:

We've been driving for five hours now.

This second example would be the version you'd use if you were on a long car trip and wanted to complain about how long you've been driving.