If you have the time, patience, and a good head for business/finance, go right ahead. If you don't, hire an agent.
I don't know how it works in Canada, but in the US almost every state requires a professional real estate licensee to complete a course and pass a state exam. For a self-seller who has the time, I suggest taking the course. Don't bother with the exam or becoming a real estate professional, but take the course. It's a couple of months of after-work classes a couple of times a week. It'll teach you what you need to know about how loans work, how to define your property line, etc., etc. It will give you the toolkit that your agent has, all for less than $1k. It just requires you to give up some of your personal time. Don't tell them why you're taking the course: they'll resent the hell out of you. Especially the instructors, who are usually moonlighting real estate professionals themselves.
You will be spending a LOT of time selling your home. It will take effort, it will take time. Don't go in expecting to sell your home within a week. If it happens that's great, but expect it to take twice as long as the average listing time for your area.
Why should you do this? On a $100k home, it'll save you the $4k of a cheap agent's fee. If you're selling a $500k home, that's $20k. That's a lot of hobbying with some seriously premium girls. If that kind of money isn't important to you then don't worry about it. But if it does matter, then be willing to do the work yourself.
Find out what homes in your neighborhood are selling for, go on an open house tour, and then dispassionately figure out what your house is actually worth.
Oh, and comparing the price between private sales and agent sales is a bullshit statistic. A LOT of private sales are between family members or people who know each other. If my parents sell me their home for $1, that counts against the stats for private sales. The stat you should pay attention to is the one found in the book Freakonomics. Homes sold by agents are consistently sold for less than the agents' homes in the same market and were on the market for a much shorter time than when agents listed those homes. Real estate agents' time vs. money earned curve is NOT the same as a home owner's. The extra $400 for an extra $10k in sales price (given the 4% commission mentioned earlier) isn't worth an extra 2 months of the agent's time and effort showing the house every Sunday, taking appointments, paying for it to stay on the MLS, fielding phone calls, etc., etc. That $10k is definitely worth an extra two months' time for most homeowners, though.
Arm yourself with information and go to war.
Edit: Oh, and Superfreakonomics has a lot of bad news for those of us in the hobby, both on the low end of streetwalkers and the high end of courtesans.