A/C Charge by Myself

I was wondering about charging My AC system by myself.

I can't recommend it. If you don't know what you're doing (for real, not just following step-by-steps in a book) it's much too easy to hurt yourself badly. It's also very easy to cause immediate and/or time-release expensive damage to your A/C system.

I have a vacuum pump I use for brake bleeding

No, sir, that is not even close to adequate. Wrong kind of vacuum pump. You need the big motor-driven kind.

and gauges that will allow me to add R134

Do you know how to interpret the readings on the gauges, by themselves and relative to each other?

Why couldn't I just vacuum the system down as much as possible and put R134 in myself

Because your brake bleeding pump won't pull anywhere near a good enough vacuum. You'll be left with noncondensibles (air and water) in the system, which will form acid that will gradually eat your condenser, evaporator, and other parts from the inside out.

It isn't so much the expense

If you can afford to have it done right, by someone correctly using the right equipment, do it!