Surface-enhanced Raman spectroscopy (SERS) with high-sensitivity performance is a very necessary detection technology. Here, we present a method for increasing the performance of SERS based on silver triangular nanoprism arrays (ATNAs) vertically excited via a focused azimuthal vector beam (AVB). The ATNA substrates with different structural parameters are prepared based on the traditional self-assembled and modified film lift-off technique. Based on a theoretical model established adopting the structural parameters of the ATNA substrates, theoretical simulation results show that AVB excitation can achieve greater electric-field enhancement than linearly polarized beam (LPB) excitation. Experimental result indicates that SERS sensitivity obtained via AVB excitation is 10 13M (1 M = 1 mol/L) using rhodamine 6G (R6G) as the target analyte, which is 2 orders of magnitude lower than that of LPB excitation (10 11M). Meanwhile, the uniformity and reproducibility of the ATNA substrates are examined using Raman mapping and batch-to-batch measurement, respectively, and the Raman enhancement factor is calculated to be ～3.3×107. This method of vector light field excitation may be used to improve the SERS performance of the substrates in fields of ultra-sensitive Raman detection.