u can try this:

(require 'smtpmail)
(setq smtpmail-debug-info t)
(setq send-mail-function 'smtpmail-send-it)
(setq message-send-mail-function 'smtpmail-send-it)
(setq smtpmail-default-smtp-server "smtp.163.com")
(setq smtpmail-smtp-server "smtp.163.com")
(setq smtpmail-local-domain "163.com")   ;; <<-
(setq smtpmail-sendto-domain "163.com")  ;; <<-

(setq smtpmail-auth-credentials  ; or use ~/.authinfo
      '(("smtp.163.com" 25 "usr" "pwd")))

-- 
Kyle

非淡泊无以明志,非宁静无以致远

More info about Kyle , [http://kyle.bloghome.cn]
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