Markov Chain Monte Carlo algorithms are often used to sample combinatorial structures such as matchings and independent sets in graphs. A Markov chain is defined whose state space includes the desired sample space, and which has an appropriate stationary distribution. By simulating the chain for a sufficiently large number of steps, we can sample from a distribution arbitrarily close to the stationary distribution. The number of steps required to do this is known as the mixing time of the Markov chain. In this thesis, we consider a number of Markov chains for sampling matchings, both in general and more restricted classes of graphs, and also for sampling independent sets in claw-free graphs. We apply techniques for showing rapid mixing based on two main approaches: coupling and conductance. We consider chains using single-site moves, and also chains using large block moves. Perfect matchings of bipartite graphs are of particular interest in our community. We investigate the mixing time of a Markov chain for sampling perfect matchings in a restricted class of bipartite graphs, and show that its mixing time is exponential in some instances. For a further restricted class of graphs, however, we can show subexponential mixing time. One of the techniques for showing rapid mixing is coupling. The bound on the mixing time depends on a contraction ratio b. Ideally, b < 1, but in the case b = 1 it is still possible to obtain a bound on the mixing time, provided there is a sufficiently large probability of contraction for all pairs of states. We develop a lemma which obtains better bounds on the mixing time in this case than existing theorems, in the case where b = 1 and the probability of a change in distance is proportional to the distance between the two states. We apply this lemma to the Dyer-Greenhill chain for sampling independent sets, and to a Markov chain for sampling 2D-colourings.