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Lightning:
How lightning is produced by convective storms is rather poorly understood. It exists because of large potential differences between regions of positive and negative charge (between the ground and clouds or from one portion of cloud to another). Current research indicates that lightning is favored by a mixture of ice crystals and subcooled liquid drops (not frozen) within a strong updraft. Lightning bolts primarily transfer a negative charge from cloud to ground but can transfer positive charge. Though most lightning flashes appear to last only a fraction of a second, many strikes are actually a series of shorter duration bolts (of which there could be 5 to 25 or more). This is the reason I have so many daytime lightning photos (see below). The thunder we hear is generated by the sudden expansion and contraction of air that is heated by the lightning bolt.
 
Lightning Safety:
One of the safest places of all (besides underground) is a car. A car is not safe because it has rubber tires (what a horrible myth); it is safe because the electrical current quickly disperses around the body of the car and into the ground very effectively (acts as a Faraday cage). A house is also quite safe but lightning has penetrated windows or traversed plumbing or electrical wires and killed people. That's why you are often told to stay off the phone and avoid showers or baths during electrical storms. If caught in the open, you should not seek cover under a tree especially lone trees in otherwise open areas. Instead your best safety measure is to crouch down (don't lie) as close to the ground as possible - hug your knees. Forget the other myth about rubber sneakers, they won't protect you in the least. This only scratches the surface of lightning safety - for more details, I highly recommend the Lightning Safety Institute website.
 
Photographing Lightning:
Photographing lightning at night is relatively easy provided you have access to remote areas away from town/city lights. One cardinal rule to obey: always focus at infinity. Anything less is plain stupidity. Associated with this rule: disable auto-focus, manually focus to infinity and do not touch it again. Here are some tips to help you:

1. Use a tripod (duh). If you don't have one, how about a simple bean bag (I always carry a few with my gear).
2. Remove any filters (UV, skylight, polarizers, etc.)
3. As suggested under General photo tips, use your lens' middle values for aperature setting (f-8 or f-11 typically have the best optics).
4. Use a cable-release cord to minimize vibrations that you would cause by pressing the shutter release on the camera body.
5. If appropriate, try using a flash to brighten the immediate foreground. I set my camera's "trailing-sync" flash mode.
6. For daytime lightning photography, be ready to waste a lot of film. Because most lightning flashes are a series of bolts not a single one, you can fire your shutter as quickly as your reflexes allow and capture a strike on film. The faster your eye-hand coordination, the better your chances.
7. If ambient light is dim and you use very slow film (which I do), then you may be able to close down your aperature and increase the time your shutter is open to capture a bolt. This is actually quite easy for storms which are producing very frequent lightning of perhaps a bolt every second or two. The leftmost photo in row 2 was taken this way - it was a 2-second exposure at f-22.
8. The last option is to build or purchase an electronic device that senses a lightning flash and triggers an electronic camera shutter to open. This isn't nearly as hard as it sounds. You can pick up a book on opto-electric circuits at Radio Shack. If your camera uses a mechanical shutter I'm afraid the task is much harder and slower.