We analyzed the structures formed by 3,3’,5,5’-tetrabromobiphenyl (TBBP) on the Au(111) surface under ultra-high vacuum (UHV) conditions using scanning tunneling microscopy. TBBP, which contains two phenyls, is expected to form the same structure after combining with other molecules with different orientations. Islands composed of three types of dimers were obtained at room temperature. Annealing of the dimers at temperatures above 423 K formed a porous nanostructure with neighboring nanohole distances of 0.7 nm, consistent with our expectations. The porous nanostructure was composed of combinations of dimers with various orientations, indicating the flexibility of the precursor molecule in forming the obtained structure. Display omitted •Tetrabromobiphenyl molecules formed a porous nanostructure by orientation adaptation.•The molecules on Au(111) surface formed islands composed of three types of dimers without additional annealing.•The annealing time influenced the formation of oligomers.•Annealing at 423 K can balance the on-surface reaction and conformational changes.