A novel method for film formation has been developed utilizing miniemulsion properties. The process destabilizes emulsion droplets in a controlled fashion and deposits the droplets onto a substrate to form a resin film. By utilizing a polymeric stabilizer with lower critical solution temperature (LCST) behavior as functional protective colloid, the emulsion is designed to destabilize when the system reaches a set temperature. Using LCST-bearing protective colloids, benzoxazine resin films are formed and polymerized. By design, the utilized polymeric stabilizer contains benzoxazine groups, which are covalently incorporated into the matrix as a reactant. The resulting film is similar to those formed following a solution casting method. The novel process offers the possibility of applying precision micro-optic coating eliminating the edge effect as well as forming homogeneous film thickness aided by the near monodisperse emulsion particle sizes.