Betweenness centrality is an important index widely used in different domains such as social networks, traffic networks and the world wide web. However, even for mid-size networks that have only a few hundreds thousands vertices, it is computationally expensive to compute exact betweenness scores. Therefore in recent years, several approximate algorithms have been developed. In this paper, first given a network G and a vertex r∈V(G), we propose a Metropolis-Hastings MCMC algorithm that samples from the space V(G) and estimates betweenness score of r. The stationary distribution of our MCMC sampler is the optimal sampling proposed for betweenness centrality estimation. We show that our MCMC sampler provides an (ϵ,δ)-approximation, where the number of required samples depends on the position of r in G and in many cases, it is a constant. Then, given a network G and a set R⊂V(G), we present a Metropolis-Hastings MCMC sampler that samples from the joint space R and V(G) and estimates relative betweenness scores of the vertices in R. We show that for any pair ri,rj∈R, the ratio of the expected values of the estimated relative betweenness scores of ri and rj respect to each other is equal to the ratio of their betweenness scores. We also show that our joint-space MCMC sampler provides an (ϵ,δ)-approximation of the relative betweenness score of ri respect to rj, where the number of required samples depends on the position of rj in G and in many cases, it is a constant.