Tritium is radioactive, but it isn't THAT nasty. Not all kinds of radioactivity are alike, and if tritium were that ugly, you can bet it wouldn't be in watches or gunsights. However, in the past, people have gotten nasty mouth cancers because as they painted with tritium-laced paint, they licked the painbrushes.
Oops.
However, any radioactive product is subject to certain specific regulations and controls. I don't know exactly what is required for tritium, but the average joe isn't able to deal with it.
And the one big dealbreaker: It is frighteningly expensive in any significant quantity. Tritium is very unstable (half-life of 12.3 years, IIRC- after 12.3 years, half of it is tritium, half is an isotope of helium), so you can't exactly stockpile it and it isn't found in nature. I am no expert, but I would think that the only way to make it is by neutron bombardment (getting hydrogen to accept 2 more neutrons isn't something done in your basement), and equipment for that sort of thing is also VERY tightly controlled (ask Iran and North Korea).
All in all, you are better off just buying the sights already made. You don't want to deal with this stuff at home.
I should probably also mention that tritium is a major component in thermonuclear weapons (used for the fusion part), so if you were trying to stock up on it, I would expect a lot of guys in black suits showing up with long lists of questions.