5-nm-scale line and hole patterning is demonstrated by synergistic integration of block copolymer (BCP) lithography with atomic layer deposition (ALD). While directed self-assembly of BCPs generates highly ordered line array or hexagonal dot array with the pattern periodicity of 28 nm and the minimum feature size of 14 nm, pattern density multiplication employing ALD successfully reduces the pattern periodicity down to 14 nm and minimum feature size down to 5 nm. Self-limiting ALD process enable the low temperature, conformal deposition of 5 nm thick spacer layer directly at the surface of organic BCP patterns. This ALD assisted pattern multiplication addresses the intrinsic thermodynamic limitations of low χ BCPs for sub-10-nm scale downscaling. Moreover, this approach offers a general strategy for scalable ultrafine nanopatterning without burden for multiple overlay control and high cost lithographic tools.