The application of steric blocking in surface science is exemplified by the control of surface patterns through the selective methylation of pentacenetetrone. Pentacenetetrones interact (with one another) on Cu(111) via intermolecular hydrogen bonding involving the carbonyl oxygen and the adjacent hydrogen atoms. Steric blocking of the intermolecular interaction by the successive insertion of inert methyl groups at terminal locations transforms a dense molecular pattern first into isolated double rows and eventually into single rows in a highly predictable fashion. Density functional theory modeling reveals the underlying energetics.