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In order to find an effective way to improve the photostability of crosslinking dyes, two novel 1 : 2 Cr-complexed crosslinking azo dyes were synthesized through diazotization and coupling reaction, chlorination, amination and metallization. The structures of the intermediate dyes were characterized by IR, MS and 1H NMR. It was confirmed that the intermediate dyes existed in hydrazone form. The structures of the Cr-complexed crosslinking dyes were characterized by FT-IR spectroscopy and atomic absorption spectroscopy. The differences of the major absorption peaks between metal-free crosslinking dyes and their corresponding Cr-complexes were studied by UV-vis spectroscopy. Silk and wool were dyed with crosslinking dyes through exhaustion dyeing without salt, and then were fixed via crosslinking agent 2-chloro-4, 6-di(aminobenzene-4′-β-sulfatoethylsu1fone)-1, 3, 5-s-triazine. The results show that the application of Cr-complexed crosslinking dyes on silk and wool exhibit high dyeing exhaustion and crosslinking reaction ratio. Moreover, the lightfastness of metallized dyes on silk and wool is 2-3 grades higher than that of the metal-free crosslinking dyes. [ABSTRACT FROM AUTHOR]