Social engineering is the practice of deceiving legitimate users of a system into disclosing information that will aid the attacker in compromising system security. A simple example is calling a user and pretending to be someone from the service desk working on a network issue; the attacker then proceeds to ask questions about what the user is working on, what file shares she uses, what her password is.
A successful social engineering act requires the trust of the victim, so user awareness training about the problem is an effective countermeasure. Strict policies about service desk staff never asking for personally identifying information or passwords over the phone or in person can also help potential victims recognize a social engineering attempt.
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