By manipulating the clustering coefficient of a network without changing its degree distribution, we examine the effect of clustering on the synchronization of phase oscillators on networks with Poisson and scale-free degree distributions. For both types of networks, increased clustering hinders global synchronization as the network splits into dynamical clusters that oscillate at different frequencies. Surprisingly, in scale-free networks, clustering promotes the synchronization of the most connected nodes (hubs) even though it inhibits global synchronization. As a result, they show an additional, advanced transition instead of a single synchronization threshold. This cluster-enhanced synchronization of hubs may be relevant to the brain that is scale-free and highly clustered.