In this research, surface plasmon resonance (SPR) spectroscopy was used for sensing copper ion by combining the SPR with nanocrystalline cellulose modified by hexadecyltrimethylammonium bromide and graphene oxide composite (CTA-NCC/GO) thin film. The binding of Cu2+ on CTA-NCC/GO thin film was monitored by using SPR spectroscopy. By using the obtained SPR curve, detection range, binding affinity, sensitivity, full width at half maximum (FWHM), data accuracy (DA), and signal-to-noise ratio (SNR) have been calculated. The results showed that the sensor detection range was 0.01 until 0.5 ppm, and that it reached a saturation value. Moreover, the resonance angle shift followed the Langmuir isotherm model with a binding affinity constant of 4.075 × 103 M-1. A high sensitivity of 3.271° ppm-1 also was obtained for low Cu2+ concentration ranged from 0.01 to 0.1 ppm. For the FWHM, the lowest value calculated was at 0.08 and 0.1 ppm, which is 3.35°. The DA of the SPR signal consecutively highest at 0.08 and 0.1 ppm. Besides that, the SNR of the SPR signal increases with the Cu2+ concentrations. The CTA-NCC/GO thin film morphological properties were also studied by using atomic force microscopy. The rms roughness values, which were obtained before and after in contact with Cu2+, were 3.51 nm and 2.46 nm, respectively.