In this paper, we investigate dynamic channel and rate selection in cognitive radio systems which exploit a large number of channels free from primary users. In such systems, transmitters may rapidly change the selected (channel, rate) pair to opportunistically learn and track the pair offering the highest throughput. We formulate the problem of sequential channel and rate selection as an online optimization problem, and show its equivalence to a {\it structured} Multi-Armed Bandit problem. The structure stems from inherent properties of the achieved throughput as a function of the selected channel and rate. We derive fundamental performance limits satisfied by {\it any} channel and rate adaptation algorithm, and propose algorithms that achieve (or approach) these limits. In turn, the proposed algorithms optimally exploit the inherent structure of the throughput. We illustrate the efficiency of our algorithms using both test-bed and simulation experiments, in both stationary and non-stationary radio environments. In stationary environments, the packet successful transmission probabilities at the various channel and rate pairs do not evolve over time, whereas in non-stationary environments, they may evolve. In practical scenarios, the proposed algorithms are able to track the best channel and rate quite accurately without the need of any explicit measurement and feedback of the quality of the various channels.