I've done plenty of work on the side over the years, but there are reasons and limits.
When my company first started doing computer and network maintenance I was very up front about the fact that I already was involved in that area, and if anything the company had a conflict of interest with me, not the other way around. They were muscling in on my turf, and I refused to sign a non-compete that had anything to do with my pre-existing activities. Non-compete on copiers was a different story - I've never moonlighted a copier, although I have fixed a few for charities where I donated my time. The goodwill factor has already been mentioned here.
Another factor is that my computer repairs don't cross into the territory where my company would be interested, or even competitive. I do people's home computers and such - the company won't touch small potatoes like that, and people won't pay the hourly rate we'd charge them. Even the local computer shops are half that price. On the flip side, a few accounts doing the kind of work my company is looking for would be a full time job, and I already got one... not interested in taking on anything that big, and we end up referring each other across that line.
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