The Continuous Plankton Recorder (CPR) survey is a valuable resource for mapping changes in plankton distribution and understanding harmful algal ecology because of its breadth and longevity. Preservation methods with formalin degrade DNA, making it difficult to use as a molecular tool for archived marine samples. DNA was extracted from CPR samples immediately after collection, seven months later and after nine years of storage from a cruise track along the Iberian Peninsula. PCR reactions performed from the nine-year timepoint were hybridized to probes in an electrochemical biosensor and compared to results obtained from RT-PCR performed at two earlier time points. The successful identification of Pseudo-nitzschia spp., Prorocentrum lima, Alexandrium minutum, Alexandrium ostenfeldii, Gambierdiscus spp. and Coolia spp. was documented. The biosensor analysis outperformed RT-PCR, allowing us to document certain tropical toxic dinoflagellates, viz., Gambierdiscus and Coolia, that produce human ciguatoxins and Coolia toxins, respectively. These non-native algal toxins can accumulate, pervade the food web and negatively impact human food security. This supports the northerly movement of microalgae with climate change in offshore Iberian peninsular waters. This study highlights biosensors as a cost-effective tool for the offshore monitoring of HAB species and advances molecular technologies for long-term CPR datasets that have limited records of harmful algae. DNA from formalin-preserved CPR samples is degraded, so the use of a short, multiprobe biosensor can augment historical plankton records with contemporary methods that also capture infrequently occurring benthic taxa carried in surface waters. The integration of probe-based biosensor technologies offers a promising avenue for exploring plankton dynamics in response to environmental changes.