1. os.system

import os
import tempfile

filename1 = tempfile.mktemp (".txt")
open (filename1, "w").close ()
filename2 = filename1 + ".copy"
print filename1, "=>", filename2

#拷文件
os.system ("copy %s %s" % (filename1, filename2))

if os.path.isfile (filename2): print "Success"

dirname1 = tempfile.mktemp (".dir")
os.mkdir (dirname1)
dirname2 = dirname1 + ".copy"
print dirname1, "=>", dirname2

#拷目录
os.system ("xcopy /s %s %s" % (dirname1, dirname2))

if os.path.isdir (dirname2): print "Success"

2. shutil.copy和shutil.copytree

import os
import shutil
import tempfile

filename1 = tempfile.mktemp (".txt")
open (filename1, "w").close ()
filename2 = filename1 + ".copy"
print filename1, "=>", filename2

#拷文件
shutil.copy (filename1, filename2)

if os.path.isfile (filename2): print "Success"

dirname1 = tempfile.mktemp (".dir")
os.mkdir (dirname1)
dirname2 = dirname1 + ".copy"
print dirname1, "=>", dirname2

#拷目录
shutil.copytree (dirname1, dirname2)

if os.path.isdir (dirname2): print "Success"

3.  win32file.CopyFile

import os
import win32file
import tempfile

filename1 = tempfile.mktemp (".txt")
open (filename1, "w").close ()
filename2 = filename1 + ".copy"
print filename1, "=>", filename2

#拷文件
#文件已存在时，1为不覆盖，0为覆盖
win32file.CopyFile (filename1, filename2, 1)
win32file.CopyFile (filename1, filename2, 0)
win32file.CopyFile (filename1, filename2, 1)

if os.path.isfile (filename2): print "Success"

dirname1 = tempfile.mktemp (".dir")
os.mkdir (dirname1)
dirname2 = dirname1 + ".copy"
print dirname1, "=>", dirname2

#拷目录
win32file.CopyFile (dirname1, dirname2, 1)

if os.path.isdir (dirname2): print "Success"

4. SHFileOperation 

import os
from win32com.shell import shell, shellcon
import tempfile

filename1 = tempfile.mktemp (".txt")
open (filename1, "w").close ()
filename2 = filename1 + ".copy"
print filename1, "=>", filename2

#拷文件
#文件已存在时，shellcon.FOF_RENAMEONCOLLISION会指示重命名文件
shell.SHFileOperation (
  (0, shellcon.FO_COPY, filename1, filename2, 0, None, None)
)
shell.SHFileOperation (
  (0, shellcon.FO_COPY, filename1, filename2, shellcon.FOF_RENAMEONCOLLISION, None, None)
)
shell.SHFileOperation (
  (0, shellcon.FO_COPY, filename1, filename2, 0, None, None)
)

if os.path.isfile (filename2): print "Success"

dirname1 = tempfile.mktemp (".dir")
os.mkdir (dirname1)
dirname2 = dirname1 + ".copy"
print dirname1, "=>", dirname2

#拷目录
shell.SHFileOperation (
  (0, shellcon.FO_COPY, dirname1, dirname2, 0, None, None)
)

if os.path.isdir (dirname2): print "Success"

不知道有没有其它的了，os.rename不算，那个是移动文件。另外我在测试它们的性能如何。
http://timgolden.me.uk/python/win32_how_do_i/copy-a-file.html 
这里和楼主列出的都一样，没有更多的了 
或者使用Chilkat  http://www.chilkatsoft.com/refdoc/pythonCkFileAccessRef.html

测试结果出来了： 
 测试环境：系统——Win7 RTM，CPU——P4 3.0，MEM——1.5G DDR400，U盘——Kingston 4G 
  
 用4种不同的方法从硬盘拷贝MSDN 2008 SP1（2.37G）到U盘： 
  
 os System      的方法耗时903.218秒 
 shutil         的方法耗时1850.634秒 
 win32file      的方法耗时861.438秒 
 SHFileOperation的方法耗时794.023秒 
  
 另外SHFileOperation是显示对话框的，可以这样用 

shell.SHFileOperation (
  (0, shellcon.FO_COPY, filename1, filename2, 
   shellcon.FOF_RENAMEONCOLLISION | \
   shellcon.FOF_NOCONFIRMATION |\
   shellcon.FOF_NOERRORUI | \
   shellcon.FOF_SILENT, None, None)
)