For online playing PES 6 , you must open port on yours router.

Online port is 5739

For detail read more  

Name - (General Description, I name this as PES - NO PROBLEM)
Protocol Select - UDP
External Port Start - 5739
External Port End 5739
Internal IP Address 192.168.x.X (ps2 or PCs ip
Internal Port 5739
To get your Ip on PC go to START RUN type CMD and then IPCONFIG , if its your PS2 then i think it defaults to 192.168.1.10 <not sure

Ensure port 5739 is selected in PES6/settings

If problem persist check your softer firewall,or WinXP/SP2 firewall

For port forwarding tutorial use this great link

Enjoy in online playing

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