In this paper, we propose a self-assembled graphene oxide (GO)/Ag NPs SERS Raman sensor based on a novel type of optofluidic MHF as a point-of-care testing (POCT) device. This device is used to diagnose jaundice and its related diseases through on-line detection of free bilirubin content in human serum. This optofluidic Raman sensor is composed of a microstructured hollow fiber (MHF) with a microstructured channel and a suspended core, which allows the sample solution to flow in the channel while interacting with the strong evanescent field on the suspended core. Here, the suspended core was modified by a GO/Ag NPs SERS substrate. When the sample flows through the channel, and interacts with the strong evanescent field generated by the suspended core, the on-line SERS signal is generated and can be coupled back to the suspended core to be detected. In addition, both the electrostatic interaction and interference between GO/Ag NPs with the target enriched bilirubin. The results show that the detection concentration range of bilirubin aqueous, bilirubin in albumin and bilirubin in human blood are all in the range of 2 μM–100 μM, and all have a good linear response. The limit of detection reaches the order of 10−6 M. This rapid, sensitive and label-free SERS Raman sensor of free bilirubin in blood can detect excessive levels of bilirubin in the actual blood environment of the human body, providing a broad prospect for clinically accurate diagnosis of jaundice and related diseases.