Buffs are great. You can wear them lots of ways. I use mine like a balaclava sometimes, as a beanie under my helmet, or as a neckwarmer.
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My top winter clothes:
1. Booties. I swear they are God's gift to winter cyclists. You can get away with booties + warm fuzzy socks + one lighter pair of inner socks down to into the 20s, especially if it's not rainy. Definitely buy booties. Just a warning: The velcro ones get un-velcro-y after a season of pulling on and off.
2. Three pairs of gloves. I wear normal fingerless gloves as a bottom layer, followed by a cheap pair of polar fleece fingered gloves (you can find them at Old Navy fairly cheap). I just do that if it's freezing or above. Much below freezing I add another pair of polar fleece gloves on top, usually a thicker pair with the grippy padding on the fingertips and palms.
3. Ear warmers of different weights. These in conjunction with a helmet keep my head plenty warm down to about 10F, which is the lowest I voluntarily ride in. I have super thick ones, medium-weight ones, and thin ones depending on the temperature.
4. Bellwether water-resistant pants. They have a water- and wind-resistant outer layer just on the tops of your thighs and front of your shins; the back part is breathable and flexible, which is nicer for riding than full GoreTex. They're also fuzzy inside and are excellent on their own for down to the high 30s or so. In mid-30s down to low 20s I wear those with a pair of long spandex as a middle layer and a pair of normal padded bike shorts as a bottom layer. The downside to this type of pants is that they let water in eventually when it's wet. However, I found that wearing all GoreTex (especially GoreTex pants) ends up feeling like wearing a rain fly despite their claims of excellent breathability, so you get all sweaty and wet inside anyway.
5. Breathable GoreTex jacket with armpit zippers. The armpit zippers are nice because you can get hot even riding in cold weather, and venting there lets you cool off easily without taking the whole thing off. I like my bike jacket because it has a "butt flap" that unbuttons to cover your posterior when it's really wet out.
6. Multiple thicknesses of long-sleeved shirts. I have a very thick warm Underarmor shirt I wear most days in the winter. If it's extra-cold I'll put on a lighter layer on top of that, and if it's super cold I'll do a third layer (but usually just the two + a jacket and my neon yellow vest keep me plenty warm). Long-sleeved jerseys aren't always the best for this because they don't work as well with jackets as I might like. I have three weights of shirts that I vary in combination together depending on the temperature, and that about does it for my upper body.
Bike accessories:
1. Bright front headlight. I just got a Light & Motion Vega, which is insanely bright, but has multiple brightness settings. It's fabulous. It takes very little time to charge up, and on the blinky mode lasts for something like 20 hours. I also have a smaller 3-LED PlanetBike front headlight just for blinking to get cars' attention.
2. Single-tube Down Low Glow. This lights you up from the side so cars see you even if you're not head-on to them; it, too, is fairly dazzling. It's also very fun to use.One caveat: It had some trouble with corrosion after I used it all winter. I had to send it back and have them give me a new one. Also it takes all night to charge up, and it has a separate big battery you have to find a spot for on your bike.
3. PlanetBike SuperFlash. This is far and away the brightest blinky rear light I've ever seen. I use all three of these when it gets to riding in the dark all the time, and so far I've not had any mishaps.
So...um...I think that's just about itBut if you want to talk more about riding in the winter, I've ridden all the way through two New England winters, so I'd be happy to give you more info if you want.
Buffs are great. You can wear them lots of ways. I use mine like a balaclava sometimes, as a beanie under my helmet, or as a neckwarmer.