A new photo-cross-linkable poly(acrylic acid) (PAA) polymer functionalized with a photoreactive benzophenone group (PAA-BP) was synthesized and examined as a binder for Si-based anodes. Upon UV irradiation, the PAA-BP binders formed an irreversible cross-linked structure through the formation of a new three-dimensional C-C bond network between the benzophenone moiety and the PAA backbone. The photo-cross-linked PAA-BP binder demonstrated a marginal volume expansion (38%) after full lithiation, compared to conventional binders and this resulted in an improved cycle performance of the Si anode over 100 cycles with a high reversible capacity of ca. 1600 mA h g(-1). We attributed this phenomenon to the enhanced mechanical properties of the photo-cross-linked PAA-BP binder, which were evaluated using nanoindentation and swelling measurements.