These datasets contains the spectral information used in a publication regarding the implementation of complexometric titrations of copper monitored using Surface Enhanced Raman Spectroscopy (SERS). In this study the sensitivity of a classic complexometric titration system for Cu2+ is pushed into the nanomolar regime thanks to SERS monitoring of the endpoint. All the data are organised as column vectors. The data consists of three csv files with semi-column separators. “AN334_and_AN338_laser_532nm_1microM_copper_variation_of_PAN_all_data_corrected_serie_11_points” correspond to spectral data acquired under 532 nm irradiation with variation of the PAN (100, 50 and 25 nM) concentration for 1 µM of copper. “AN335_and_AN341_laser_532nm_500nM_copper_variation_of_PAN_all_data_corrected_serie_11_points” correspond to spectral data acquired under 532 nm irradiation with variation of the PAN (100, 50 and 25 nM) concentration for 500 nM of copper. “AN336_and_AN344_laser_532nm_250nM_copper_variation_of_PAN_all_data_corrected_serie_11_points” correspond to spectral data acquired under 532 nm irradiation with variation of the PAN (100, 50 and 25 nM) concentration for 250 nM of copper. Each dataset has 90 685 rows corresponding to 1 irradiation used (532 nm), 2 experimental replicate titration series including 1 titration + 1 blank titration for each titration and for 3 differents concentrations of PAN and 11 titration steps per titration series. For the 3 copper concentrations we obtain 396 samples. The columns vectors consist of a first sub-vector of spectral descriptors (identity of spectra, identity and composition of measurement samples and conditions of spectral acquisition), followed by a sub-vector of baseline-subtracted spectral intensities. The meaning of each column is in the .docx file titled "Structure of AN334-AN338 to AN336-AN344 datasets”. The other two csv fils with semi-column separators "AN339_AN342_AN345_laser_638nm_variation_of_copper_and_PAN_all_data_corrected_serie_11_points" and "AN340_AN343_AN346_laser_785nm_variation_of_copper_and_PAN_all_data_corrected_serie_11_points" correspond to spectral data acquired under 638 and 785 nm irradiation respectively. In both files, the data correspond to the 11-point experiments with PAN variation (100, 50 and 25 nM) and copper variation (1 µM, 500 and 250 nM). Finally, the data consists of one csv files with semi-column separators. “AN384_to_AN386_Laser_532_638_785nm_all_data_corrected_titration_serie_20_points” correspond to spectral data acquired under 532, 638 and 785 nm irradiation. The dataset has 111 241 rows corresponding to 3 irradiations used (532, 638 and 785), 2 replicate titration series + 1 blank titration and 20 titration steps per titration series. The columns vectors consist of a first sub-vector of spectral descriptors (identity of spectra, identity and composition of measurement samples and conditions of spectral acquisition), followed by a sub-vector of baseline-subtracted spectral intensities. The meaning of each column is in the .docx file titled "Structure of AN384 to AN386 datasets”.