Photon-counting detectors can increase the range of underwater optical wireless communication (UWOC) by enhancing the detection sensitivity and have thus become an active research area in recent years. However, system performance still needs to be improved in the reported underwater photon-counting communication (UPCC) experiments. In this study, a real-time, high-speed UPCC system was designed and experimentally validated based on a single-photon avalanche diode (SPAD). A reliable symbol synchronization method based on pulse-position modulation (PPM) was developed. This method achieved slot synchronization by using a narrow-pulse-width laser and a simple matched filter and realizes frame synchronization through an improved synchronization sequence. In addition, channel errors were corrected by serially concatenated convolutionally coded PPM (SCPPM), and digital signals were processed in real time based on field-programmable gate arrays (FPGAs). Finally, desktop communication experiments were completed at a slot frequency of 25 MHz and a communication rate of 6.21 Mbps. The system exhibited a bit error rate (BER) of less than 10 -7 , a received optical power of only -84.3 dBm, and an efficiency of 1.35 photons per bit.