The spatial distribution of localized surface plasmon resonance (LSPR) plays a key role in many plasmonic applications. Based on the thermal stability of alumina templates, this work reports a novel approach to manipulate the distribution of LSPR and exhibits its significance for an important plasmonic application, the surface-enhanced Raman spectroscopy (SERS). A suitable thermal annealing sharpens the edges in top surfaces (far from the substrates) of Ag nanoparticles, which significantly strengthens the distal mode (DM) with the LSPR excited on the top surfaces. Because the top surface is the major place to adsorb probe molecules, this manipulation greatly improves the detection sensitivity of SERS. Our research provides a new way to improve the sensitivity of SERS, which also indicates that great care has to be taken on special LSPR mode which is largely responsible for a certain plasmonic application (e.g., the DM for SERS although it is not the major mode).