Self-assembled monolayers (SAMs) of alkylsiloxanes were patterned by microcontact printing (mu CP) on a number of substrates : Al/Al2O3, Si/SiO2, TiN/TiO2, glasses, indium tin oxide (ITO), and plasma-modified polyimide. The patterned SAMs on these surfaces define and direct the selective chemical vapor deposition (CVD) of copper using (hexafluoroacetylacetonato)(vinyltrimethylsilane)copper(I)(Cu-I(hfac)(vtms)) as the source gas. This paper presents several examples of microstructures of copper fabricated by selective, SAM-directed CVD, including fabrication of thin-film interconnects (with feature sizes of 0.5-100 mu m), and selective filling of trenches and vias (models of microstructures having high aspect ratios) with feature sizes below 1 mu m.