On my recent trip, the reciprocity fee was required of citizens of only four countries and the US was not one of them. These countries were easily identified by their flags in the immigration area of the SCL airport (if this is your country’s flag, turn left here): Albania, Australia, Canada and Mexico.
Edit: Note that the reciprocity fee has been removed for US citizens – see Is there still reciprocity fee at Chile airport entry for US citizens? (after US Visa waiver) for more details.
Original answer, still correct for citizens of some countries :
Officially I believe the fee is payable no matter how you enter the country, however the simple truth is that it’s only collected at Santiago International Airport, and it’s only collected on arrival.
If you do not enter via SCL, then you will NOT have to pay the reciprocity fee – regardless of how you do enter the country (land, water, or air via another airport). It is not collected on exit, even if you didn’t pay it on entry so you can still depart from SCL without having to pay.
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