In this paper, we are interested in symbiotic radio networks, in which an Internet-of-Things (IoT) network parasitizes in a primary network to achieve spectrum-, energy-, and infrastructure-efficient communications. Specifically, the BS serves multiple cellular users using time division multiple access (TDMA) and each IoT device is associated with one cellular user for information transmission. We focus on the user association problem, whose objective is to link each IoT device to an appropriate cellular user by maximizing the sum rate of all IoT devices. However, the difficulty in obtaining the full real-time channel information makes it difficult to design an optimal policy for this problem. To overcome this issue, we propose two deep reinforcement learning (DRL) algorithms, both use the historical information to infer the current information in order to make appropriate decisions. One algorithm, centralized DRL, makes decisions for all IoT devices at one time with global information. The other algorithm, distributed DRL, makes a decision only for one IoT device at one time using local information. Finally, simulation results show that the two DRL algorithms achieve comparable performance as the optimal user association policy which requires perfect real-time information, and the distributed DRL algorithm has the advantage of scalability.Index Terms-Symbiotic radio networks (SRN), ambient backscatter communication (AmBC), user association, deep reinforcement learning.