Essential Climate Variables (ECVs) like ocean colour provide crucial information on the Optically Active Constituents (OACs) of seawater, such as phytoplankton, non-algal particles, and coloured dissolved organic matter (CDOM). The challenge in estimating these constituents through remote sensing is in accurately distinguishing and quantifying optical and biogeochemical properties, e.g., absorption coefficients and the concentration of chlorophyll a (Chla), especially in complex waters. This study evaluated the temporal and spatial variability of bio-optical properties in the coastal waters of the Western Iberian Coast (WIC), contributing to the assessment of satellite retrievals. In situ data from three oceanographic cruises conducted in 2019–2020 across different seasons were analyzed. Field-measured biogenic light absorption coefficients were compared to satellite estimates from Ocean-Colour Climate Change Initiative (OC-CCI) reflectance data using semi-analytical approaches (QAA, GSM, GIOP). Key findings indicate substantial variability in bio-optical properties across different seasons and regions. New bio-optical coefficients improved satellite data retrieval, reducing uncertainties and providing more reliable phytoplankton absorption estimates. These results highlight the need for region-specific algorithms to accurately capture the unique optical characteristics of coastal waters. Improved comprehension of bio-optical variability and retrieval techniques offers valuable insights for future research and coastal environment monitoring using satellite ocean colour data.