We show femtosecond direct laser-induced assembly of gold nanostructures with plasmon resonance band variable as a function of laser irradiation in a wide range of visible wavelengths. A system of 2-photon lithography is used to achieve site-selectively controlled dewetting of a thin gold film into nanostructures in which size and shape are highly dependent on the laser power. Simultaneous measurements of localized surface plasmon resonance (LSPR) and surface enhanced Raman scattering (SERS) in the presence of various concentrations of trans-1,2-bis(4-pyridyl) ethylene (BPE) as target molecule are performed in order to highlight the relationship between structural dimensions, plasmonic effect, and detection activity. The resulting gold NPs exhibit high sensitivity as both LSPR and SERS sensors and allow the detection of picomolar concentrations of BPE with a SERS enhancement factor (SEF) of 1.33 × 109 and a linear detection range between 10-3 and 10-12 M.