Visible light communication (VLC) based on a light-emitting diode (LED) is considered to be a potential candidate for the next-generation communication. In this paper, a novel Zadoff–Chu matrix transform (ZCT) precoding is proposed to improve the performance of the traditional space-time block coding- (STBC-) based multiple-input multiple-output and orthogonal frequency division multiplexing (MIMO-OFDM) system. Compared with the existing orthogonal circulant matrix transform (OCT) precoding scheme, the proposed ZCT precoding achieves a much lower peak-to-average power ratio (PAPR) while maintaining the advantage of the uniform signal-to-noise ratio (SNR), which reduces the performance loss caused by LED nonlinearity. To study the system performance further, we set up an experimental demonstration to verify performance improvement under the condition of different driving peak-to-peak voltages (Vpps) and direct current (DC) offsets. Experimental results show that ZCT precoding gains the best bit error rate (BER) performance compared with the traditional and the OCT precoding MIMO-OFDM systems, whose BER is always below the 7% pre-forward error correction (pre-FEC) threshold of 3.8 × 10 −3.