<h3>Purpose/Objective(s)</h3> To study the linear energy transfer (LET) effect upon rib fracture (RF) in breast cancer patients treated with pencil-beam scanning proton therapy (PBS) using dose-linear energy transfer volume histogram (DLVH). <h3>Materials/Methods</h3> After IRB approval, we retrospectively identified RF cases detected after workup of chest wall pain or incidentally on imaging in breast cancer patients treated with PBS to the breast/chest wall and regional nodes from 2015-2020. Control patients were selected to match the RF patients 2:1 considering prescription dose, boost location, reconstruction status, laterality, chest wall thickness, and treatment year. For all plans, a chest wall was contoured, incorporating ribs and intercostal muscles within the 50% prescription isodose line. Both dose and LET were calculated using a planning tool dose engine. DLVH was generated for each patient, using dose and LET as the two axes. The DLVH index, <i>V</i>(<i>d, l</i>), defined as <i>V</i>(% for normalized volume or cc for absolute volume) of the structure with a dose of at least <i>d</i> Gy[RBE] and an LET of at least <i>l</i> keV/µm, was calculated for all combinations of <i>d</i> and <i>l</i>. Conditional logistic regression model was used to establish the relation of <i>V</i>(<i>d, l</i>) and the observed RF at each combination of <i>d</i> and <i>l</i>. The derived <i>p values</i> constitute a <i>p value</i> map in the 2D dose and LET plane. Concordance and its standard error (se) maps were generated to evaluate the performances for all DLVH indices. A correlation coefficient map was obtained to determine the correlation between the featured DLVH indices. <h3>Results</h3> Eight RF cases were identified, and 16 controls were matched. Of RF patients, seven were treated with post-mastectomy (PMRT) and one was treated with post-lumpectomy radiotherapy. Six RF patients treated with PMRT received a dose of 50 Gy[RBE] in 25 fractions to the chest wall and regional lymph nodes; of these, four received a simultaneous integrated boost (SIB) of 56.25 Gy[RBE] to the chest wall (n=2) or axillary nodes (n=2), and one received a sequential boost of 14 Gy[RBE] in 7 fractions to the chest wall. One RF patient that received PMRT was treated with 40.05 Gy[RBE] in fifteen fractions to the chest wall and regional lymphatics. The post-lumpectomy patient received 50 Gy[RBE] in 25 fractions to the whole breast and regional nodes with a SIB of 56.25 Gy[RBE] to the lumpectomy cavity. Two characteristics correlated with RF (<i>p</i><0.2): 1) Smaller <i>V</i>(50-54 Gy[RBE], 0-4.4keV/µm) of the RF patients with a maximum concordance of 0.813 (se 0.114); 2) Larger <i>V</i>(0-36 Gy[RBE], 5.2-6.8keV/µm) of the RF patients with a maximum concordance of 0.875 (se 0.119) compared with controls. These two features were independent from each other with a weak negative correlation (-0.185). <h3>Conclusion</h3> The increase of high LET in moderate dose regions of the chest wall from constraining the adjacent heart and lung dose during PBS treatment planning may result in increased risk of RF.