Compared with traditional radio frequency (RF)based techniques, the advantages of wider bandwidth, higher security, and stronger electromagnetic immunity (EMI) capability make visible light communications (VLC) a good candidate technology for the 6th generation (6G) wireless communications. Red, green, and blue (RGB) light-emitting diodes (LEDs) based VLC has become an important research branch due to its low price and high reliability. However, the saturation of photodiode (PD) caused by the ambient background light may seriously degrade the bit error rate (BER) performance of an RGB-VLC system's three spatially uncoupled information streams (i.e., red, green, and blue LEDs can transmit different data packets simultaneously) in practical applications. To mitigate the ambient light interference in point-to-point RGB-VLC systems, we propose, PNC-VLC, a network-coded scheme that uses two LEDs with the same color at the transmitter to transmit two different data streams and we make use of the naturally overlapped signals at the receiver to formulate physical-layer network coding (PNC). The adaptivity of PNC-VLC could effectively improve the BER degradation problem caused by the saturation of PD under the influence of ambient light. We conducted simulations based on the parameters of commercial off-the-shelf (COTS) products to prove the superiority of the PNC-VLC under the influence of four typical illuminants. Simulation results show that the PNC-VLC system can maintain a better and more stable system BER performance under different ambient background light conditions. Remarkably, with 2/3 throughput efficiency, PNC-VLC can bring 133.3% gain to the BER performance when compared with the traditional RGB-VLC systems under the Illuminant A interference model, making it a good option for VLC with unpredictable ambient background interferences.