With the increasingly fierce market competition, offering a free trial has become a potent stimuli strategy to promote products and attract users. By providing users with opportunities to experience goods without charge, a free trial makes adopters know more about products and thus encourages their willingness to buy. However, as the critical point in the promotion process, finding the proper adopters is rarely explored. Empirically winnowing users by their static demographic attributes is feasible but less effective, neglecting their personalized preferences. To dynamically match the products with the best adopters, in this work, we propose a novel free trial user selection model named SMILE, which is based on reinforcement learning (RL) where an agent actively selects specific adopters aiming to maximize the profit after free trials. Specifically, we design a tree structure to reformulate the action space, which allows us to select adopters from massive user space efficiently. The experimental analysis on three datasets demonstrates the proposed model's superiority and elucidates why reinforcement learning and tree structure can improve performance. Our study demonstrates technical feasibility for constructing a more robust and intelligent user selection model and guides for investigating more marketing promotion strategies.