Q:

Use of "Align with"

Would you prefer to define your goals, then find a work which align with it?
The use of "align with" is at right place here?
Or, would you prefer to suggest something else?

A:

I would not use "align" in this sentence, but there is more I would change.
I am not completely sure about what you mean with the first part of your sentence, but since it is grammatical, I will leave it unchanged.

find a work

Assuming that you mean "the work that someone does for a living", the word you are looking for is a job, or maybe employment.

which align with it

You are using align here as a verb, in which case it would take an extra s. However, no native speaker would say it like this. You can have a job in line with your goals.
"It" is singular, but you are referring to multiple goals, so it should be plural.
So the whole sentence would become

Would you prefer to set your goals, then find a job in line with them?

To align means "to bring in line", so you could use the verb "align" in a sentence with a similar meaning like this:

Maybe you want to align your job with your goals.

