This work first demonstrates polymorph control of amino acids by optical trapping with high-repetition-rate (80 MHz) femtosecond (fs) laser pulses. A saturated aqueous solution of L-serine (L-Ser) is irradiated by laser pulses to trigger crystallization, and the polymorphism of the resultant crystals is systematically investigated as a function of laser power and polarization. Irradiating near the contact line (three-phase point) of the solution triggers L-Ser crystallization, either at the laser focus or away from the laser focus. In-situ Raman spectroscopy for all the generated crystals reveals that fs laser irradiation yields two types of L-Ser polymorphs, which are identified as monohydrate and anhydrous forms (Form 1 and Form 2, respectively). When the average laser power is constant, only leftcircular polarization produces Form 1 with a 60% probability, whereas all other polarizations, linear and right-circular polarization, produce Form 2 with 100% probability. The dynamics of this unique polymorphism depending on the handedness of the circular polarization and the mechanism behind it are discussed in terms of the trapping efficiency of the pre-nucleation (liquid-like) clusters, which depends on the differences in refractive index and the arrangement of the liquidlike clusters reflecting the given laser polarization.