The synthesis and second-order nonlinear optical (NLO) properties of a new family of optically nonlinear coumarin dye-containing polymers is reported. Polymerizable coumaromethacrylate (CMA) monomers having various alkyl spacers (C2 to C5) between the polymerizable group and the chromophore were prepared and copolymerized with methylmethacrylate (MMA) and other vinyl monomers. The CMA copolymers had high chromophoric content (up to 18 × 1020) and glass transitions as high as 132°C. Spin cast films were prepared on BK7 substrates and oriented by corona-onset poling at elevated temperatures (COPET). The poled CMA copolymer films were characterized for spectroscopic absorption and second harmonic properties. A comparison of the nonlinear optical properties of poled CMA-MMA copolymers to poled guest-host systems is made. Relative to guest/host systems, CMA-MMA copolymer films exhibit larger and much more stable second-order nonlinear optical properties.