We report the first observation of diffractively produced open charm in 800−GeV/c pp collisions of the type pp→pD*X. We measure cross sections of σdiff(D*+)=(0.185±0.044±0.054)μb and σdiff(D*−)=(0.174±0.034±0.029)μb. Our measurements are based on 4.3×109 events recorded by FNAL E690 in the fixed-target run of 1991. We compare our results with previous fixed-target charm experiments.