Superposed constellation combined with spatial multiplexing multiple-input multiple-output (MIMO) techniques have been increasingly utilized in visible light communication (VLC) systems, as multiplexing gains can be achieved regardless of the correlation extent of the VLC channel. Herein, we propose a novel superposed 64-quadrature amplitude modulation (QAM) constellation scheme for 2 × 2 MIMO VLC systems. Considering the nonlinearity of light-emitting diodes (LEDs), two geometrically shaped 8QAM constellations are introduced to reduce the peak-to-average power ratio at the transmitter. Because the two 8QAM constellations are superposed in an interleaved manner, the required power ratio between two transmitted signals is 1, which further reduces the risk of nonlinear distortion and avoids signal-to-noise ratio deterioration induced by power competition. The proposed superposed 64QAM constellation scheme is experimentally investigated comprehensively, where the system performance is evaluated under different transmitted powers, direct current bias currents, and driving peak-to-peak voltages (Vpps). The experimental results show that the proposed scheme achieves better bit error rate (BER) performance than the traditional superposed 64QAM constellation schemes. Below the 7% pre-forward error correction BER threshold of 3.8 × 10-3, the dynamic range of the driving Vpps of the two LEDs improves from 0.06 to 0.4 V and 0.23 to 0.4 V when the optimal power ratio is achieved.