Linear and nonlinear optical properties of a new soluble polymer bearing distyrylbenzene chromophore, the alkoxy-sulphono-substituted p-phenylenevinylene oligomer (MTPV-ORSO) attached as a side-chain to the methyl methacrylate backbone are reported. This chromophore was developed for introduction into single-mode nonlinear optical polymer fibres. The molecular second-order and third-order nonlinearities were estimated with quantum chemical calculations (MOPAC). The side-chain polymer shows an optical absorption maximum at 326 nm. The polymer was incorporated into the core of the fibre preform with a procedure which led to a step index profile, as measured with a preform profiler, suitable for a single-mode optical fibre. Second harmonic of the fundamental 1200 nm wave was measured in the corona poled polymer films giving the second-order susceptibility d33 = 0.8 pm/V for the polymer containing about 1.3 wt% of the side-chain chromophore and 0.1 pm/V in a guest-host system containing 0.24 wt% of the chromophore in the fibre preform. The coherence length of the side-chain polymer, equal to 28 µm at 1200 nm, was evaluated from the dispersion of the linear refractive indices. Degenerate four-wave mixing (DFWM) with amplified femtosecond pulses was also applied to measure the nonlinear refractive index of the co-polymer at 800 nm.