Its a structure where each item in the structure has two children.
Each item can hold a value, perhaps a string or number, and each value has not more than two values under it.
They are used mainly in sorting/indexing and are not something you would normally use in everyday vb6 programming. They are more associated with low level C++ programming, where you are doing somthing like sorting or indexing a lot of random data.
By storing the data in a tree, instead of in a linear format, it is faster to find things. You just go down the branches of the tree, branching off in the right direction until you find what you want. This is faster than going through a file from one end to the other.