This one is from Venezuela. The Scott catalogue says stamps inscribed "Correos" were for external postage and those inscribed "Instruccion" were for internal postage and revenue. Furthermore, these Instruccion stamps were invalid as of 1895, and your copy is from a printing after 1895. Your stamp is similar to the 5c of 1893, Scott #128.
Here is some information on early stamps of Venezuela. I don't see a date on the information, but it seems like it might be very old (as in 100+ years).
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