Laser-induced breakdown spectroscopy (LIBS) is characterized as a powerful tool in in-situ online analysis with its fast and multiple detecting abilities. But in the area of detecting trace sample in aqueous solution of low concentration, the turbulence, scattering, absorbance and cooling effect of liquid medium limits its performance. Traditional method includes liquid jet, liquid-solid transformation and pre-concentration on other medium, yet the procedure of sample preparation is complicated and time consuming. In this work, we propose a new method to achieve pre-concentration, in which filter paper and electro-spray ionization (ESI) are used. In our experiment, we choose MnSO4 as sample. The surface of filter paper is sprayed with MnSO4 aqueous solution of different concentration by an ESI. The pulsed laser is focused on the surface of filter paper and the plasma is formed in the focusing area. Through an optical fiber the spectrum of plasma is detected by a spectrometer. The ESI system, pulses generator system and the UI on PC are home-made. The spectra lines of Mn at 257.6nm, 259.4nm and 260.6nm are analyzed. Results show that the limit of detection at 257.6nm is sub-ppb and the R2 of calibration curve is more than 0.93. Compared with traditional method, like soak and drip processing, our method can increase the concentration of the sample by simply expanding spraying time, achieving a higher signal-to-noise ratio (SNR) and a lower limit of detection (LOD). In addition, the consumption of sample solution is as low as several hundred μl in each detection.