Classical recommendation methods typically face the filter bubble problem where users likely receive recommendations of their familiar items, making them bored and dissatisfied. To alleviate such an issue, this applied paper introduces a novel framework for personalized serendipitous recommendation in an e-commerce platform (i.e., JD.com), which allows to present user unexpected and satisfying items deviating from user’s prior behaviors, considering both accuracy and novelty. To achieve such a goal, it is crucial yet challenging to recognize when a user is willing to receive serendipitous items and how many novel items are expected. To address above two challenges, a two-stage framework is designed. Firstly, a DNN-based scorer is deployed to quantify the novelty degree of a product category based on user behavior history. Then, we resort to a potential outcome framework to decide the optimal timing to recommend a user serendipitous items and the novelty degree of the recommendation. Online A/B test on the e-commerce recommender platform in JD.com demonstrates that our model achieves significant gains on various metrics, 0.54% relative increase of impressive depth, 0.8% of average user click count, 3.23% and 1.38% of number of novel impressive and clicked items individually.