A novel 3D point cloud learning model for deep LiDAR odometry, named PWCLO-Net, using hierarchical embedding mask optimization is proposed in this paper. In this model, the Pyramid, Warping, and Cost volume (PWC) structure for the LiDAR Odometry task is built to hierarchically refine the estimated pose in a coarse-to-fine approach. An attentive cost volume is built to associate two point clouds and obtain the embedding motion information. Then, a novel trainable embedding mask is proposed to weight the cost volume of all points to the overall pose information and filter outlier points. The estimated current pose is used to warp the first point cloud to bridge the distance to the second point cloud, and then the cost volume of the residual motion is built. At the same time, the embedding mask is optimized hierarchically from coarse to fine to obtain more accurate filtering information for pose refinement. The pose warp-refinement process is repeatedly used to make the pose estimation more robust for outliers. The superior performance and effectiveness of our LiDAR odometry model are demonstrated on the KITTI odometry dataset. Our method outperforms all recent learning-based methods and outperforms the geometry-based approach, LOAM with mapping optimization, on most sequences of the KITTI odometry dataset.