To implement a calibration sample by which an incident angle can be measured with high accuracy, an electron beam adjustment method, and an electron beam apparatus using the calibration sample. To adjust an electron beam using a calibration sample, the calibration sample includes a silicon single crystal substrate 201 whose upper surface is a {110} plane, a first recess structure 202 opening in the upper surface and extending in a first direction, and a second recess structure 203 opening in the upper surface and extending in a second direction intersecting the first direction, in which the first recess structure and the second recess structure each include a first side surface and a first bottom surface that intersects the first side surface, and a second side surface and a second bottom surface that intersects the second side surface, the first side surface and the second side surface are {111} planes, and the first bottom surface and the second bottom surface are crystal planes different from the {110} planes.