I can't really think of many good reasons to use mirrors as reflectors. First they are inefficient; the reflective surface is on the rear surface, so any light must travel through the glass to the reflective surface then back through the glass in a usable direction. Someone stated rear surface mirrors are 80% efficient, I believe when this question came up on another board that number was closer to 65%. You only approach 80 - 90% with a coated front surface mirror such as a specular aluminum reflector. Mirrors are certainly more dificult to make into the correct form for an efficient reflector, and much heavier. Just lining your canopy with mirrors won't make for a good reflector, and quite possibly will be dangerous. Lastly I suspect it could be expensive to puchase the mirrors to make a reflector only to end up with an inferior finished product.
To me the trade off is this, purchase (or build) good quality, proven design reflectors, and get more light where it's supposed to be, or DIY something inferior and use higher wattage lighting to get your desired results, and pay for it the entire life of your system.