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Go to a place called "Scrapyard", it's quite a ways north/northeast of megaton, just past an above ground subway railing thingy that's about as high as a highway. Scrapyard is a huge junk yard, run around it 'til you find Dogmeat fighting a couple raiders, once the raiders are dead, just ask Dogmeat to join you. He'll be the best video game friend you've ever had.
See also What is dogmeat in the game Fallout 3?