Pretty incredible for its time. It's a little unlike modern Metroidvania games because there is an overworld map to break up the action, but the concept remains the same. Tough-ass action platforming, large world size, great gameplay. Controls take a bit of time to get used to.
"The last Metroid is in captivity. The galaxy is at peace." Subsequently, all hell breaks loose and Samus descends to Planet Zebes for the final showdown with Ridley. This is the gold standard against which all other Metroid games are compared. Play it. Avaliable on Wii U eShop if you are one of the 5 people with one.
The Addams Family
A surprisingly AWESOME metroidvania experience. While there are no permanent character "enhancements" like new moves or armor, the game is packed with non-linear goodness. There are extra alternative sections where players who reach the boss are rewarded with a permanent health boost, however! The real neat thing about this game: there are secret areas EVERYWHERE. EVERYWHERE. Even the Game Over screen has a secret room in it! This game is goofy, fun, and full of neat things worth experiencing.
First Person Metroid, and masterfully done. Get these if you already have a Gamecube, otherwise get the remastered editions in Metroid Prime Trilogy for the Wii, because the wiimote makes the first-person shooty bits eleven times better.
Little-known Metroidvania, you run around beating up pigs and doing tasks. Awesome! Known as Tombi! in Europe.
Tomba! 2: The Evil Swine Return
See above, only now with polygons and hair-tearingly difficult minigames (MINECART). You can also retrieve a savegame from Tomba! to unlock a secret quest. Both it and the prequel are horrifically difficult to find, but are available on PSN for a fairly cheap price. Known as Tombi! 2 in Europe.