In the present work, binary and ternary complexes of silver nanoparticles (AgNPs) with bisacetylacetoneethylenediamine (bis-AAED) reagent and cetyltrimethylammonium bromide (CTAB) were synthesized. UV–Vis analysis showed that AgNPs exhibited a plasmon resonance peak at 410 nm, while bis-AAED displayed π→π* and n→π* absorption bands at 223, 270, and 299 nm. The Ag–bis-AAED complex revealed shifted bands at 227, 272, and 308 nm, whereas the Ag–bis-AAED–CTAB ternary complex exhibited sharper and more intense peaks at 227, 272, and 308 nm, confirming complex formation and changes in the electronic environment. According to XRD results, the bis-AAED reagent exhibited 2θ peaks within 9.90°–42.88° with an average crystallite size of 26.0 nm; the Ag–bis-AAED binary complex showed 2θ peaks at 37.78° and 43.91° with an average size of 10.9 nm; and the Ag–bis-AAED–CTAB ternary complex displayed 2θ peaks within 12.30°–43.95° with an average crystallite size of 9.0 nm. The broadening of peaks and decrease in intensity indicate the partially amorphous nature of the complexes.