Actually, with default sort order (ASCENDING) NULL values come last.
Logic dictates that the sort order be reversed with the DESCENDING keyword, so NULLs come first in this case.
But the best part comes last: you can choose which way you want it:
Quoting the current manual, version 9.3 as of writing:
If NULLS LAST is specified, null values sort after all non-null
  values; if NULLS FIRST is specified, null values sort before all
  non-null values. If neither is specified, the default behavior is
  NULLS LAST when ASC is specified or implied, and NULLS FIRST when DESC
  is specified (thus, the default is to act as though nulls are larger
  than non-nulls). When USING is specified, the default nulls ordering
  depends on whether the operator is a less-than or greater-than operator.
Bold emphasis mine.