A photoassisted citrate reduction reaction under blue LEDs is an easy and highly reproducible method to synthesize high-yield decahedral silver nanoparticles (AgNPs) in the absence of seeds in the initial photochemical reaction. In this study, icosahedral AgNPs with sizes of 80 to 150 nm could be synthesized by using the photoassisted tartrate reduction method under UV light with a wavelength of λ=(310±12) nm. The product yield of icosahedral AgNPs is higher than 90 %. SAED (selected-area electron diffraction) patterns and XRD (X-ray diffraction) spectra show that these AgNPs have multiply twinned structures. High-resolution TEM and dark-field TEM show that the facet of the triangular planes of these icosahedral AgNPs is {111}. This is the first report of icosahedral AgNPs synthesized by using a seed-free photochemical method. SERS (surface-enhanced Raman scattering) of Crystal Violet (CV) measurements show that the as-prepared icosahedral AgNP colloids have excellent SERS enhancement factors, which are approximately four and six times the enhancement factors of decahedral AgNP colloids and thermal-citrate-reduction AgNP colloids, respectively.