When Tom Walker comes upon the Devil, Tom is not at all shaken. He is not afraid in the slightest, in part because his wife is such a difficult woman that he is used to this kind of abuse. He in fact tells the Devil that the Devil should not be on Deacon Peabody's lands, which is a brazen way for a person to deal with the Devil. While most people would be terrified of coming upon the Devil on such a dark night, Tom is almost defiant.

Tom's reaction to the Devil shows that he lacks the normal responses of most people and lacks the conscientiousness and human qualities that would make him fear the sacrifice that the Devil demands of him. However, Tom lacks a conscience and is not afraid of sin or evil, so he agrees to the Devil's evil deal.

Tom encounters the Devil (who he names as "Old Scratch", an outdated slang term for the Devil) while taking a shortcut through the woods, and resting for a moment near a ruined "Indian fort" - though it is little more than a burial ground at this point. As the reader, the setting of the fort is given a great deal of foreboding Gothic imagery that makes it seem hostile and evil, but Tom doesn't seem to mind. 

At first, Tom is surprised by the appearance of the Devil, but mostly because he hadn't thought anyone else was around, and because the Devil has a distinct appearance unlike any person Tom has met - black skin, red eyes, and so forth - but Tom quickly settles into his typical mannerisms. 

We might assume that any normal person, upon encountering the Devil, might be surprised, shocked, fearful or in awe. Tom, however, behaves as if the Devil were like any other person. This indicates that Tom is probably brave and foolish, and he has not learned to fear evil as others might.