As an important imaging modality, mammography is considered to be the global gold standard for early detection of breast cancer. Computer-Aided (CAD) systems have played a crucial role in facilitating quicker diagnostic procedures, which otherwise could take weeks if only radiologists were involved. In some of these CAD systems, breast pectoral segmentation is required for breast region partition from breast pectoral muscle for specific analysis tasks. Therefore, accurate and efficient breast pectoral muscle segmentation frameworks are in high demand. Here, we proposed a novel deep learning framework, which we code-named PeMNet, for breast pectoral muscle segmentation in mammography images. In the proposed PeMNet, we integrated a novel attention module called the Global Channel Attention Module (GCAM), which can effectively improve the segmentation performance of Deeplabv3+ using minimal parameter overheads. In GCAM, channel attention maps (CAMs) are first extracted by concatenating feature maps after paralleled global average pooling and global maximum pooling operation. CAMs are then refined and scaled up by multi-layer perceptron (MLP) for elementwise multiplication with CAMs in next feature level. By iteratively repeating this procedure, the global CAMs (GCAMs) are then formed and multiplied elementwise with final feature maps to lead to final segmentation. By doing so, CAMs in early stages of a deep convolution network can be effectively passed on to later stages of the network and therefore leads to better information usage. The experiments on a merged dataset derived from two datasets, INbreast and OPTIMAM, showed that PeMNet greatly outperformed state-of-the-art methods by achieving an IoU of 97.46%, global pixel accuracy of 99.48%, Dice similarity coefficient of 96.30%, and Jaccard of 93.33%, respectively.