Answer: No, you shouldn’t report both 46221 (Hemorrhoidectomy, internal, by rubber band ligation[s]) and 46250 (Hemorrhoidectomy, external, 2 or more columns/groups) for the scenario you describe.
A Correct Coding Initiative (CCI) edit lists 46221 as a column 2 code for 43250 with a modifier indicator of “0,” which means that you cannot override the edit pair and report the codes together under any circumstances.
Way out: CPT® provides different hemorrhoidectomy codes for mixed procedures like you described. You can report your surgeon’s removal of one internal and one external hemorrhoid by ligation using 46260 (Hemorrhoidectomy, internal and external, 2 or more columns/groups).