The facile synthesis of shape-controlled Pd nanoparticles (PdNPs) with ascorbic acid as a reducing agent and cetyltrimethylammonium bromide (CTAB) as a capping agent is presented in this study. The synthesized PdNPs were characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman Spectroscopy. The prepared PdNPs show efficient surface-enhanced Raman scattering (SERS) properties. SERS studies on the adsorption characteristics of 1,4-phenylene diisocyanide (1,4-PDI) on colloidal PdNPs have revealed that the relative peak intensity of the (NC)_free and (NC)_bound modes distinctly depends on the 1,4-PDI concentration as well as the shape of the PdNPs. Furthermore, we found that the PdNPs are also efficient photoelectron emitters such that the SERS spectrum of 4-nitrobenzenethiol (4-NBT) on PdNPs is readily converted to that of 4-aminobenzenethiol (4-ABT) under 632.8 nm radiation.