Successful implementation of process analytical technology (PAT) hinges on the ability to make continuous or frequent measurements in-line or at-line of critical product attributes such as composition and particle size, the latter being an important parameter for particulate processes such as suspensions and emulsions. A novel probe-based spatially and angularly-resolved diffuse reflectance measurement (SAR-DRM) system is proposed. This instrument, along with appropriate calibration models, is designed for online monitoring of concentration of chemical species and particle size of the particulate species in process systems involving colloidal suspensions. This measurement system was investigated using polystyrene suspensions of various particle radius and concentration to evaluate its performance in terms of the information obtained from the novel configuration which allows the measurement of a combination of incident light at different angles and collection fibres at different distances from the source fibres. Different strategies of processing and combining the SAR-DRM measurements were considered in terms of the impact on partial least squares (PLS) model performance. The results were compared with those obtained using a bench-top instrument which was used as the reference (off-line) instrument for comparison purposes. The SAR-DRM system showed similar performance to the bench top reference instrument for estimation of particle radius, and outperforms the reference instrument in estimating particle concentration. The investigation shows that the improvement in PLS regression model performance using the SAR-DRM system is related to the extra information captured by the SAR-DRM configuration. The differences in SAR-DRM spectra collected by the different collection fibres from different angular source fibres are the dominant reason for the significant improvement in the model performance. The promising results from this study suggest the potential of the SAR-DRM system as an online monitoring tool for processes involving suspensions.