Aryl homocoupling reactions via meta- and ortho-selective C-H activation have been achieved on surfaces, but the highly important para-selective C-H activation has not been reported yet. Combined with scanning tunneling microscopy, time-of-flight secondary ion mass spectrometry and density functional theory, here we describe dehydrogenative homocoupling of tetrafluorobenzene on Pd(111) via para-selective C-H activation to form perfluorinated oligo(p-phenylene)s.