So you've decided that your stuff isn't worth selling, but you aren't ready to toss it in the trash. As long as you can pack it into your car and drive it over to your closest thrift store (some do pickups, too), that's still a possibility. You're rid of it, but you also have no idea what will happen to it.
Will it become someone else's treasure, or will it languish by the displays of VCRs and slow cookers? There's something poetic in that, but maybe you want a more concrete idea of what happens to your stuff. Most thrift stores donate their proceeds to charities and often employ people in need, but you can also find niche charities.
Overrun with books? See if your local library or schools would be interested in taking them off your hands. Even if they don't enter the collection, they could be sold to raise funds. Habitat for Humanity will often accept extra building materials such as leftover paint or extra tiles. Nice business attire could go to a charity that helps disadvantaged men and women seeking work, and those old bridesmaid dresses (depending on how old they are, of course) might work well for a teenager who otherwise couldn't afford a prom dress. You can often recycle old electronics.
Basically, if you get to Googling, you can probably find a creative way to liberate yourself of stuff. Keep in mind that some of these methods might require you to spend money on gas or postage, though. My favorite: My local animal shelter will gladly accept towels and blankets to line cages.
In some ways, Freecycle is easier than thrift stores because you don't have to leave your house. People have come to pick up items from me that I was 100 percent sure I'd be stuck hauling to the landfill. You just join a local chapter (which usually functions as an e-mail list or an online group) and follow their instructions for offering items. You can be as arbitrary about choosing takers as you like. This option does involve somebody coming by your house, but your stuff is gone and all you had to do was send an e-mail.
If none of these options works, there's still one that some people swear by: setting your gear out on the curb. Obviously, it depends on what it is and whether you have a homeowner's association that frowns on this sort of thing, but you might be surprised by what disappears before the garbage truck has a chance to take it.
My final words of wisdom: act decisively and fast, with no regrets. If it's sentimental but needs to go, take a picture. It doesn't take long for the best of decluttering intentions to go awry. And it's only stuff, anyway.