Explicit determination of the mean first-passage time (MFPT) for the trapping problem on complex media is a theoretical challenge. In this paper, we study random walks on the Apollonian network with a trap fixed at a given hub node (i.e., node with the highest degree), which are simultaneously scale-free and small-world. We obtain the precise analytic expression for the MFPT that is confirmed by direct numerical calculations. In the large system size limit, the MFPT approximately grows as a power law function of the number of nodes, with the exponent much less than 1, which is significantly different from the scaling for some regular networks or fractals such as regular lattices, Sierpinski fractals, T-graph, and complete graphs. The Apollonian network is the most efficient configuration for transport by diffusion among all the previously studied structures.