When it comes to outdoor natural lighting, there isn't a time of day I like shooting more than Golden Hour. My main regret is that it never seems to last long enough.
Golden Hour, as you're probably aware, is that magical time of day occurring for an hour or so before the sun sets and the color temperatures become warmer and warmer, casting a very appealing golden hue. (It's also called Magic Hour, especially by cinematographers.) Golden Hour is a particularly awesome time of day for shooting portraits of all kinds. The warm tones of Golden Hour can be especially dramatic and alluring when shooting nudes, what with all that skin showing and all.
More often than not, I shoot at Golden Hour with the sun behind the model. Doing so creates beautiful, warm, glowing edges around them. Occasionally, I shoot with the model facing into the sun, as seen in the image of Dahlia (left) I snapped at El Mirage Dry Lake, Victorville, CA, a year or two ago.
Bringing along a reflector is a good idea for Golden Hour shoots. Often, when orienting subjects with the Golden Hour sun directly behind them, you might need to bounce back some of the sun's waning light to get the kind of exposure you're looking for. Doing that, of course, depends on the look and feel you're hoping to achieve with your images. I often use a gold reflector to further enhance the already golden hues of the sun at that time of day. If, like me, you have a fold-up reflector with more than one surface color, you might experiment with gold, silver, and white surfaces reflecting the light back at the model. This will let you see how each one effects the model in different ways, color-wise. You can also shoot with the help of a strobe for fill. If so, you might want to gel the strobe with something warm to match the warm colors of the day. CTO (Color Temperature Orange) gels are one such choice. There are other gels, like Bastard Amber and Straw, you might decide to use.
Shadows during Golden Hour are long and pronounced and can add terrific aesthetic value to Golden Hour images. For those of you who like capturing distinctive flares, Golden Hour offers exceptional opportunities to do so when the sun is somewhere behind your subject and you frame and compose to capture flares.
During Golden Hour, as the sun continues to move lower and lower in the sky, lighting conditions can change quickly. You'll likely need to make periodic adjustments to your exposure to compensate. Course, that's part of what makes it so much fun to shoot at this time of day, besides the cool photos you will snap.
Below is a Golden Hour shot I snapped of Roxanne about ten years ago. (Ten years ago? Holy crap!) I used a gold reflector to enhance the already golden hues which are abundant in the image. Wow! My Photoshop hand was fairly heavy back then, especially applying Gaussian Blur to the model's face. (Click either image to enlarge.)