A four green transverse magnetic (TM)/red transverse electric (TE) light wavelength demultiplexer device, based on multi slot-waveguide (SW) structures is demonstrated. The device aims to demultiplex wavelengths in the green/red light range with wavelengths of 530, 540, 550, and 560 nm; 630, 640, 650, and 660 nm. This means that the device functions as a 1 × 4 demultiplexer for each polarization mode (TE/TM). The controlling of the light switching between two closer segment SWs under the TM/TE polarization mode was studied by designing a suitable SW structure and setting the right segment length to fit the coupling lengths of the operating wavelengths. The device is composed of six-segment SW units and six S-bends (SB) SW. The key SW and SB parameters were optimized and determined by a full vectorial beam propagation method (FV-BPM). Results show power losses better than 0.138 dB, crosstalk better than −21.14 dB, and an optical spectrum smaller than 9.39 nm, with an overall compact size of 104.5 µm. The device can be integrated in wavelength division multiplexing (WDM) for increasing data bit rate in a visible light communication (VLC) system.