Enabling energy-efficient and long-distance wireless networking is expected by various Internet-of-Things systems and consumer electronics applications. Low Power Wide Area Networks can commendably satisfy this requirement because of their combination of low-power and long-range features. Thereinto, open-standard Long Range Wide Area Network (LoRaWAN) is the representative player with hundreds of deployment cases worldwide. Unfortunately, current multiple access (MA) strategy for LoRaWAN has been proved to incur severe wireless signal interference under large-scale deployment. This is the inherent hindrance for current LoRaWAN to support large-scale wireless networking. In this context, this article aims to provide a detailed tutorial of MA issues in large-scale LoRaWAN for the first time. We start with several practical use cases of large-scale LoRaWAN. We then explain the detailed challenges of large-scale LoRaWAN networking. Representative MA solutions for better LoRaWAN networking are then described and compared. Future research directions for enhanced MA protocol design are also discussed.