Road runoff is contaminated by various micropollutants and may be treated using low impact development techniques, such as stormwater biofilters. Better understanding the processes, such as filtration, sorption and leaching, which affect pollutants in these systems is essential to reliably predicting treatment performance and optimizing system design. Field data from an in situ monitoring campaign, wherein dissolved and particulate concentrations of a wide range of micropollutants (trace metals, polycyclic aromatic hydrocarbons, bisphenol-A, alkylphenols and phthalates) were characterized in untreated road runoff and biofilter outlets for 19 rain events, are used to explore transport and retention processes. Although retention of the particulate phase of pollutants was generally quite effective, unusually high particle concentrations were observed at biofilter outlets for three winter events. Particle characterization in road runoff and outlet waters revealed that this degraded performance was due to poor filtration rather than particle erosion, which was attributed to the relative abundance of small (<10 μm) particles during this period, along with possible preferential flows. Dissolved pollutants were less effectively removed in general. To better understand this behavior, field results were combined with laboratory sorption and leaching tests. Dissolved concentrations of trace metals were shown to be influenced by organic carbon; leaching from road-originated particles may also influence their transport. Removal of the dissolved phase of organic micropollutants was limited by the contamination of the filter media, either before installation or during the first period of operation, due to emissions from construction materials.