The monitoring of invasion/permeation hydrogen on entry/exit surfaces of cathodically charged SUS316 columnar crystals was conducted with a scanning Kelvin probe force microscope (SKPFM) under atmospheric pressure. Columnar crystal specimens covered with oxide films on their surfaces under room conditions were prepared for cathodic charging tests and subsequent SKPFM measurements. The invaded hydrogen on the entry surface was detected at the δ-ferrite phases for 7 d after charging, and the segregation of invaded hydrogen at the boundaries between the δ-ferrite and austenite matrix was prolonged for >10 d after charging. The permeated hydrogen on the exit surface was detected at the δferrite phases for 3 d after charging, but was not substantial at some of the δ-ferrite phases regardless of the charging. Segregation of permeated hydrogen at the boundaries between the δ-ferrite and some of the intermetallic precipitates was prolonged for 7 d after charging. The behaviors of invaded/permeated hydrogen based on heterogeneous microstructures are discussed to improve understanding of the hydrogen embrittlement mechanism in weld metals.