Significance: Due to patients' respiratory movement or involuntary body movements during breast cancer radiotherapy, the mismatched adjacent fields in surface exposure regions could result in insufficient dosage or overdose in these regions, which would lead to tissue injury, excessive skin burns, and potential death. Cherenkov luminescence imaging (CLI) could be used to effectively detect the matching information of adjacent radiation fields without extra radiation or invasive imaging. Aim: Our objective was to provide a biological experimental basis for monitoring matching of adjacent radiation fields between photon and electron fields due to introduced shifts during radiotherapy by CLI technique. Approach: A medical accelerator was used to generate photon and electron fields. An industrial camera system was adopted to image the excited CLI signal during irradiation of chicken tissue with yellow (group A and group C experiments) or black color (group B experiment). The following introduced shifts were tested: 10, 5, 2, and 0 mm toward superior or inferior direction. A model was introduced to deal with matching error analysis of adjacent radiation fields due to introduced shifts with adapted plans used to treat neoplasms of the right breast with supraclavicular nodes or internal mammary lymph node. Results: The matching values between photon and electron fields were consistent with the tested introduced shifts during yellow chicken irradiation. In group A, average discrepancies were 0.59 ± 0.35 mm and 0.68 ± 0.37 mm for photon fields and electron fields in anterior/posterior (AP) direction, with 87% and 75% of measurement within 1 mm, respectively. In group C, average discrepancies were 0.80 ± 0.65 mm and 1.07 ± 0.57 mm for oblique photon field with gantry angles of 330 deg and 150 deg, with 66% and 65% of measurement within 1 mm, respectively. The average discrepancies were 0.44 ± 0.30 mm for electron field in the AP direction, with 94% of measurement within 1 mm. The matching error introduced by the proposed method was less than 1.5 mm for AP fields and 2 mm for oblique incidence fields. However, the field matching could not be monitored with black chicken tissue irradiation due to a weak CLI signal that could hardly be extracted from background noise in group B. Conclusions: CLI is demonstrated for the quantitative monitoring of the field match line on light biological tissue phantoms and has potential for monitoring of field matching in surface tissue during breast cancer radiotherapy. © The Authors. Published by SPIE under a Creative Commons Attribution 4.0 Unported License. Distribution or reproduction of this work in whole or in part requires full attribution of the original publication, including its.