Polystyrene and poly(vinyl alcohol) nanofibres containing cellulose nanocrystals (CNCs) were successfully produced by electrospinning. Knowledge of the local orientation of CNCs in electrospun fibres is critical to understand and exploit their mechanical properties. The orientation of CNCs in these electrospun fibres was investigated using transmission electron microscopy (TEM) and Raman spectroscopy. A Raman band located at ~1095 cm⁻¹, associated with the C–O ring stretching of the cellulose backbone, was used to quantify the orientation of the CNCs within the fibres. Raman spectra were fitted using a theoretical model to characterize the extent of orientation. From these data, it is observed that the CNCs have little orientation along the direction parallel to the axis of the fibres. Evidences for both oriented and non-oriented regions of CNCs in the fibres are presented from TEM images of nanofibres. These results contradict previously published work in this area and micromechanical modelling calculations suggest a uniform orientation of CNCs in electrospun polymer fibres. It is demonstrated that this explains why the mechanical properties of electrospun fibre mats containing CNCs are not always the same as that would be expected for a fully oriented system.