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I'm a cyclist and love the longer rides.
These days I'm pretty careful on nutrition to avoid hitting the wall and if I'm honest haven't actually hit the wall in a while.
I'm informed that endurance can be increased to allow you to go "longer on less".
What training techniques are specifically good at increasing this kind of endurance?
The big trouble with "hitting the wall" is that your body does physiologically react differently, and you need to train for that transition and working under the "post-wall" stress.
The best way of doing this is "bonk training". Bonk is the runners term for the act of hitting the wall, and training and aiming to bonk means you are prepared when it happens during cardio activity.
Commonly bonk training involves cardiovascular exercise on an empty stomach first thing in the morning, when glycogen store levels are low, as well as consuming coffee or caffeine equivalent to 2 or 3 cups of coffee and running or cycling at a casual pace (60% of max heart rate) for 20-90 minutes.
Hitting the wall means that your liver is running out of glycogen. This doesn't mean that you are completely out of energy, because your body can still burn fat. But burning fat is a harder way to get energy. In order to improve your body's ability to deal with hitting the wall, you should go on some longer rides 1-2 times per week and cycle until you hit the wall. Over time your muscles will learn to store more glycogen, and your body will also get more efficient at burning fat.
By the way, here is an excellent Wikipedia Article which discusses hitting the wall and ways to avoid it. Other than training as mentioned above, you can try carbohydrate loading, taking in some supplements while cycling, and lowering your pace to burn more fat instead of glycogen.
Well, it's pretty simple. Pretty much any training that you do that improves your aerobic capacity will increase your fat-burning potential. Interval training is a traditional - and successful - way of doing this.
If you increase your aerobic capacity, you can generate more power from fat and will therefore need to use less carbohydrate for a given power level. However, most cyclists just use this increase to ride faster, so it's a bit of a wash. If you watch pro racers - who have epic ability to burn fat - you'll notice they are sucking down the carbs pretty much all the time.
Two other answers mention bonk training. The research around the effect of riding with low glycogen stores isn't very clear - some studies say it helps, other say no. If you do want to do it, there is no requirement, however, that you go all the way to the bonk.
