Yeah... the current popular theory about ADHD is that it results from inadequate arousal of the cortex -- the "thinking brain" that we humans have in abundance. This allows more primitive subcortical emotional parts of the brain to have control more often, leading to the inability to control attention. A good piece of evidence for this is that animals with their cortexes (actually it's cortices) removed seem like ultra-ADD kids -- they can't control their behavior, have no attention span, and jump rapidly from one behavior to another.
Anyways, the cortex is believed to stimulated by a couple ascending circuits, mainly involving norepinephrine. Acetylcholine (Ach) also functions as a general arousing transmitter in the cortex, though, and so activing Ach receptors would tend to alleviate this condition. Nicotine acts at some Ach receptors (in fact these receptors are called nicotinic receptors). So it's not too surprising that ADHD people would 'self-medicate' via smoking... or so the reasoning goes.
For more info see:
Biederman J, Spencer T. (1999) Attention-deficit/hyperactivity disorder (ADHD) as a noradrenergic disorder. Biol Psychiatry 46:1234-1242.
Cook EH et al. (1995) Association of attention-deficit disorder and the dopamine transporter gene. Am J Human Genetics 56:993-998.