The integration of intermittent renewables presents significant challenges for power system operators. Sub-hourly Unit Commitment (UC) has been suggested to quickly respond to electricity supply and demand changes. It, however, poses greater complexity than hourly UC because of increased temporal resolution and complicated inter-period dependencies. Machine Learning (ML) holds high expectations for solving sub-hourly UC, but it may still face challenges in requiring heavy training burden, learning vast combinatorial possibility, and struggling to ensure feasibility. To this end, this paper presents a novel learning-tooptimize approach that synergistically combines ML with decomposition frameworks. Our approach adopts the Surrogate Absolute-Value Lagrangian Relaxation (SAVLR) framework since its decomposition leads to easier learning by drastically reducing combinatorial complexity. Then, a generic ML model embedding Gated Recurrent Units (GRUs) and Attention in the encoder-decoder structure is developed to efficiently predict subproblem solutions. The features of GRUs and Attention allows the model to capture temporal dependencies and reduce training effort across varying subproblems. Additionally, a rule-based feasibility layer is incorporated to improve feasibility w.r.t unitlevel constraints. The effectiveness of our approach is demonstrated on the IEEE 118-bus system.