ABSTRACT An analysis is presented of the optical polarimetric and multicolour photometric (BVRJ) behaviour of the blazar PKS 2155–304 during an outburst in 2010. This flare develops over roughly 117 d, with a flux doubling time τ ∼ 11 d, which increases from blue to red wavelengths. The polarization angle is initially aligned with the jet axis but rotates by roughly 90° as the flare grows. Two distinct states are evident at low and high fluxes. Below 18 mJy, the polarization angle takes on a wide range of values, without any clear relation to the flux. In contrast, there is a positive correlation between the polarization angle and flux above 18 mJy. The polarization degree does not display a clear correlation with the flux. We find that the photopolarimetric behaviour for the high flux state can be attributed to a variable component with a steady power-law spectral energy distribution and high optical polarization degree (13.3 per cent). These properties are interpreted within the shock-in-jet model, which shows that the observed variability can be explained by a shock that is seen nearly edge-on. Some parameters derived for the relativistic jet within the shock-in-jet model are: B = 0.06 G for the magnetic field, δ = 22.3 for the Doppler factor, and Φ = 2.6° for the viewing angle.