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Windows FW gives you a basic firewall. It covers applications connecting to/from remote IPs. You cannot configure specific ports, identify trusted networks or applications, set exclusions, provide a hierarchy of control
Along with the McAfee Agent and ePO, HIPS provides you a stateful firewall and intrusion prevention taking advantage of combined research from recognized security experts and coordinating that information with the CVE / CAN database list from places like Mitre.org. HIPS provides you the ability to creat custom signatures, declare Trusted Networks, identify Trusted Applications, create policy catalogs, set Location Aware Groups, add more granular protection from certain malware threats, takes advantage of both a host- and network-based intrusion prevention/detection.
If you add the recent development of the TAT (Threat Activity Tracer https://community.mcafee.com/docs/DOC-4231 - unsupported presently) you have an extremely in-depth level of protection not seen in Windows Firewall.