This study presents a novel approach for the rapid fabrication of conductive nano/microscale metal structures on flexible polymer substrate (polyimide). Silver film is simultaneously synthesized and patterned on the polyimide substrate using an advanced continuous wave (CW) laser direct writing technology and a transparent, particle-free reactive silver ion ink. The location and shape of the resulting silver patterns are written by a laser beam from a digitally controlled micromirror array device. The silver patterns fabricated by this laser direct synthesis and patterning (LDSP) process exhibit the remarkably low electrical resistivity of 2.1 μΩ cm, which is compatible to the electrical resistivity of bulk silver. This novel LDSP process requires no vacuum chamber or photomasks, and the steps needed for preparation of the modified reactive silver ink are simple and straightforward. There is none of the complexity and instability associated with the synthesis of the nanoparticles that are encountered for the conventional laser direct writing technology which involves nanoparticle sintering process. This LDSP technology is an advanced method of nano/microscale selective metal patterning on flexible substrates that is fast and environmentally benign and shows potential as a feasible process for the roll-to-roll manufacturing of large area flexible electronic devices.