LibSVM uses the one-against-one approach for multi-class learning problems. From the FAQ:
Q: What method does libsvm use for multi-class SVM ? Why don’t you use the “1-against-the rest” method ?
It is one-against-one. We chose it after doing the following comparison: C.-W. Hsu and C.-J. Lin. A comparison of methods for multi-class support vector machines, IEEE Transactions on Neural Networks, 13(2002), 415-425.
“1-against-the rest” is a good method whose performance is comparable to “1-against-1.” We do the latter simply because its training time is shorter.