The synthesis and structure of a novel ortho-fluoroazobenzene, methyl 4-bromo-3-((2,6-difluorophenyl)diazenyl) benzoate is described. The title molecule crystallizes in the centrocemetric space group P-1 with two rotomer molecules of the title compound in the asymmetric unit. The position of ortho-fluoro azo rings differ between the two rotomers with one molecule having a rotation angle of 4.4° and the other molecule having a rotation angle of 76.9° with respect to the methyl 4-bromobenzoate. Due to the tight packing the pure molecule was not seen to be photoactive. However, in solution the absorption bands in the visible region show a separation of about 20 nm as expected for o-fluoroazobenzene. A comparison to related and previously published co-crystals of substituted azobenzenes are presented. The structure of a novel ortho-fluoroazobenzene, methyl 4-bromo-3-((2,6-difluorophenyl)diazenyl) benzoate reveals the presence of two crystallographically unique rotomers in the lattice, and although the molecule is photoactive in solution, the close-packed lattice appears to inhibit photo-induced structural reorganization in the crystalline state.