This paper presents an energy-efficient and high-accuracy sampling synchronization approach for real-time synchronous data acquisition in wireless sensor networks (saWSNs). A proprietary protocol based on time-division multiple access (TDMA) and deep energy-efficient coding in sensor firmware is proposed. A real saWSN model based on 2.4 GHz nRF52832 system-on-chip (SoC) sensors was designed and experimentally tested. The obtained results confirmed significant improvements in data synchronization accuracy (even by several times) and power consumption (even by a hundred times) compared to other recently reported studies. The results demonstrated a sampling synchronization accuracy of 0.8 μs and ultra-low power consumption of 15 μW per 1 kb/s throughput for data. The protocol was well designed, stable, and importantly, lightweight. The complexity and computational performance of the proposed scheme were small. The CPU load for the proposed solution was <2% for a sampling event handler below 200 Hz. Furthermore, the transmission reliability was high with a packet error rate (PER) not exceeding 0.18% for TXPWR ≥ −4 dBm and 0.03% for TXPWR ≥ 3 dBm. The efficiency of the proposed protocol was compared with other solutions presented in the manuscript. While the number of new proposals is large, the technical advantage of our solution is significant.