Different types of rural settlement agglomerations have been formed and mixed in space during the rural revitalization strategy implementation in China. Discriminating them from remote sensing images is of great significance for rural land planning and living environment improvement. Currently, there is a lack of automatic methods for obtaining information on rural settlement differentiation. In this paper, an improved encoder–decoder network structure, ASCEND-UNet, was designed based on the original UNet. It was implemented to segment and classify dispersed and clustered rural settlement buildings from high-resolution satellite images. The ASCEND-UNet model incorporated three components: firstly, the atrous spatial pyramid pooling (ASPP) multi-scale feature fusion module was added into the encoder, then the spatial and channel squeeze and excitation (scSE) block was embedded at the skip connection; thirdly, the hybrid dilated convolution (HDC) block was utilized in the decoder. In our proposed framework, the ASPP and HDC were used as multiple dilated convolution blocks to expand the receptive field by introducing a series of dilated rate convolutions. The scSE is an attention mechanism block focusing on features both in the spatial and channel dimension. A series of model comparisons and accuracy assessments with the original UNet, PSPNet, DeepLabV3+, and SegNet verified the effectiveness of our proposed model. Compared with the original UNet model, ASCEND-UNet achieved improvements of 4.67%, 2.80%, 3.73%, and 6.28% in precision, recall, F1-score and MIoU, respectively. The contributions of HDC, ASPP, and scSE modules were discussed in ablation experiments. Our proposed model obtained more accurate and stable results by integrating multiple dilated convolution blocks with an attention mechanism. This novel model enriches the automatic methods for semantic segmentation of different rural settlements from remote sensing images.