Ordered array of Au semishells on TiO(2) spheres with controlled size are prepared by combining the nanosphere self-assembly and atomic layer deposition (ALD). This ordered 2-D structure with designed array of metal nanogaps can be used as an ultrasensitive surface-enhanced Raman scattering (SERS) substrate with high reproducibility and stability. More importantly, the SERS substrates are recyclable, as enabled by their self-cleaning function due to the TiO(2) photocatalytic degradation of the target molecules. The high SERS sensitivity and recyclability are demonstrated by the detection of Rhodamine 6G (R6G) and brilliant cresyl blue (BCB) molecules. As both the nanosphere lithography and ALD are scalable processes, such 2-D ordered substrates may find applications in chemical sensing.