Pin connections are one of the most important connecting forms and they have been widely used in engineering fields. In its service, pin connections are subject to wear, and it will be beneficial if the health condition of pin connections can be monitored in real time. In this paper, an acoustic emission (AE)-based method was developed to monitor wear degree of low rotational speed pin connections in real time in a nondestructive way. Most pin connections are operated at low rotational speed. To facilitate the research, an experimental apparatus to accelerate the wear test of low rotational speed pin connections was designed and fabricated. The piezoceramic AE sensor was mounted on the test apparatus in a nondestructive way, and it was capable of real-time monitoring. Accelerated wear tests of low rotational speed pin connections were conducted. To verify the results of the AE technique, a VHX-600E digital (from Keyence, Osaka, Japan) microscope was applied to observe the micrographs of the tested pins. The experimental results show that AE activity existed throughout the entire wear process, and it was the most prominent in the serious wear phase. The wear degree of the pin connections can be reflected qualitatively by the signal strength and the accumulative signal strength of the AE signals. In addition, two different wear forms can be distinguished by comparing the signal strength values of all specimens. Micrographs of all specimens confirm these results, and determine that the two wear forms include adhesive wear and abrasive wear. Furthermore, AE results demonstrated that adhesive wear is the main mode of wear for the low rotational speed pin connections, and the signal strength of the adhesive wear is around 190 times larger than that of abrasive wear. This feasibility study demonstrated that the developed acoustic emission technique can be utilized in the wear monitoring of pin connections in real time in a nondestructive way.