An ever increasing variety of synthetic chemicals and their metabolites are being released into environmental waters, monitoring a few dozen chemicals seems increasingly inadequate. The lack of data on their presence means polar and ionisable substances would still often be considered emerging contaminants despite making up around half of all registered synthetic compounds and having behaviours which may be hazardous to human and ecological well-being. Partition coefficient (LogP) is used for the identification of polar compounds but this does not account for the pH dependence of ionisable compounds, missing a large portion of charged compounds. Distribution coefficient (LogD) as an alternative allows for environmentally relevant pHs to be represented and the corresponding ionised compounds to be included. With a LogD of ≤0 compounds can be defined as very Polar and Ionisable Compounds (vPICs) which show strongly hydrophilic behaviour, necessitating improved techniques for their sampling and analysis. With waterway sampling dominated primarily by grab sampling and sample concentration approaches such as multi-residue solid-phase-extraction (SPE), vPICs may be missed due to incompatibility with extraction phases used and/or temporal fluctuations. Passive sampling techniques utilising various solid phases have the potential to become a complimentary monitoring tool for vPICs to better understand and account for contamination in our waterways. Current passive sampling methods have limited applicability for vPIC detection due to inadequate uptake, there is clear potential for the use of innovative receiving phases to improve monitoring, whether new sorbents, improved diffusive membranes or completely new methods such as water itself as the receiving phase. Here we present the results of uptake and extraction of a broad range of vPICs across a variety of sorbent phases.