The previous post I wrote was primarily for a standard DSL/cable modem router, not a VPN router.
I think Fubar's example might possibly work for your brother, but you should try it and see how it works. It's possible it may not work.
I think the default gateway of the NIC which connects via VPN should be the remote IP address (WAN address) of the VPN server of your brothers company, since the tunnel is XP PC NIC to VPN server. (If your brother's employer has internet access, he should still be able to access the web via his VPN. This is inefficient though since all internet/web traffic is then routed through the VPN and company connections. If they use a Proxy server and/or firewall, he would need to get with them to find out how to access the internet through the company routers, etc.)
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I have no idea if the two NIC concept will work. But I think it's great to try new things that could significantly improve working conditions/environments, so if I had the same problems, I would try it! The primary benefit of the two NIC method if successful, would be faster internet access (not encrypted). The major detriment is that this opens potential holes to the employers network through his router or 2 NIC setup (depending on method). He should use packet filtering to decrease the the potential security holes that his dual NIC or 'opened' router would introduce while accessing the employer's resources via VPN.
To try the two NIC method, this is what I would do:
1>>Install the second NIC.
2>>If a DHCP server is used on the DSL/cable modem router, then I would disable the DHCP server and set static IP addressess for the local devices (IP hosts like his PC NICs). Try to separate both NIC IP addresses into separate networks.
For example 192.168.1.10 is on one network if the netmask is 255.255.255.0 while 192.168.2.10 is on another network. (If his original NIC was using a dynamic, private IP address via the DHCP server like the two listed above and he changes the IP addresses to static IPs, he may need to change the address settings on the VPN server at his company to whatever corresponds on his PC for future VPN access.)
3>>Set the second NIC to use the DSL/cable modem router local address as the gateway (the side connected to your LAN, not the side connected as the WAN port to the ISP). This address might be something like 192.168.0.1.
4>>Set the DNS servers on the second NIC to be the ISP DNS servers. Make sure 'Use Default Gateway for remote network' is selected on the second NIC (you can also try it deselected to prevent changes to the routing/metric table). Internet access should now be available through the second NIC (if not originally available/routed through the original NIC used on the VPN.)
5>>On the NIC for VPN access, de-select the option to "Use the default gateway for remote network", but on the NIC for internet access, ensure option to "Use the default gateway for remote network" is enabled.
6>>Packet filter each NIC if possible. The PPTP protocols are TCP 1723 and IP 47 and should be set to permit only on the NIC for VPN access. TCP/UDP 80, 8080, 8008, 443 would be the protocols to permit on the second NIC if he only needs to browse the web. This would ensure the greatest security for your brothers employer without using a firewall.
7>>Ensure IE uses the LAN to access the Internet, not another dial-up connection or any VPN connection in the Network and Dial-up connections (also viewable under IE connections).
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You may still have to adjust metrics, since whenever the VPN connects while the "Use Default Gateway on remote network" is enabled, it should automatically set the VPN route to the lowest metric. With the "Use default gateway on remote network" option disabled, the metric table should not be updated, but I'm not sure. I haven't tested this, sorry. But I would also ensure that both NICs have the same metric (without Default Gateway enabled on both as a last attempt.)
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I still have no idea if the dual NIC method will work.