Stable nitronyl nitroxide radical and imino nitroxide radical were incorporated into the benzene rings of novel photochromic 7,7′-dimethyl-[2,2′-bi-1H-indene]-3,3′-diethyl-3,3′-dihydroxy-1,1′-dione (1), leading to the synthesis of novel multifunctional compounds 4 and 5. The photochromic properties, ESR spectroscopy and magnetic properties of the title compounds were investigated. Compounds 4 and 5 possess visible photochromism upon photoirradiation, and their ESR signals undergo secular broadening after photoirradiation. The magnetic susceptibility measurement shows that the antiferromagnetic interaction of 4 and 5 becomes stronger after photoirradiation. In compounds 4 and 5 there are two kinds of spin centers after photoirradiation: one is nitroxide radical, and the other is photo-generated radicals from two indanone moieties. Our results demonstrated that the colour and magnetic properties of compounds 4 and 5 could be modulated by photoirradiation.