Rational design of sulfur electrodes is exceptionally important in enabling a high specific energy lithium/sulfur cell. Constructing a continuous pore structure of the sulfur electrode that enables facile lithium ion transport into the electrode and mitigates the reconstruction of sulfur is a key factor for enhancing the electrochemical performance. Here, we report a three-dimensionally (3D) aligned sulfur electrode prepared by directional freeze tape casting. The 3D aligned sulfur-graphene oxide (S-GO) electrode consisting of a few micron-thick S-GO layers with 10-20 μm interlayer spacings demonstrates significant improvement in the performance of the Li/S cell. Moreover, the freeze tape cast graphene oxide electrode exhibits homogenous reconfiguration behaviour in the polysulfide catholyte cell tests, and demonstrated extended cycling capability with only 4% decay of the specific capacity over 200 cycles. This work emphasizes the critical importance of proper structural design for sulfur-carbonaceous composite electrodes.