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It is important to determine the relationship between the concentration of chlorophyll a (Chla) and the inherent optical properties (IOPs) of ocean water to develop optical models and algorithms that characterize the biogeochemical properties and estimate biological pumping and carbon flux in this environment. However, previous studies reported relatively large variations in the particulate backscattering coefficient (b bp (λ)) and Chla from more eutrophic high-latitude waters to clear oligotrophic waters, especially in oligotrophic oceanic areas where these two variables have little covariation. In this study, we examined the variability of b bp (λ) and Chla in the euphotic layer in oligotrophic areas of the tropical Western Pacific Ocean and determined the sources of these variations by reassessment of in-situ measurements and the biogeochemical-argo (BGC-Argo) database. Our findings identified covariation of b bp (λ) and Chla in the water column below the deep Chla maximum (DCM) layer, and indicated that there was no significant correlation relationship between b bp (λ) and Chla in the upper layer of the DCM. Particles smaller than 3.2 µm that were in the water column above the DCM layer had a large effect on the b bp (λ) in the vertical profile, but particles larger than 3.2 µm and smaller than 10 µm had the largest effect on the b bp (λ) in the water column below the DCM layer. The contribution of non-algal particles (NAPs) to backscattering is up to 50%, which occurs in the water depth of 50 m and not consistent with the distribution of Chla. Phytoplankton and NAPs were modeled as coated spheres and homogeneous spherical particles to simulate the b bp (λ) of the vertical profile by Aden-Kerker method and Mie theory, and the results also indicated that the backscattering caused by particles less than 20 µm were closer to the measured data when they were below and above the DCM layer, respectively. This relationship also reflects the b bp (λ) of particles in the upper water was significantly affected particle size, but b bp (λ) in the lower water was significantly affected by Chla concentration. This effect may have relationship with phytoplankton photoacclimation and the relationship of a phytoplankton biomass maximum with particle size distribution in the water column according to the previous relevant studies. These characteristics also had spatial and seasonal variations due to changes of Chla concentration at the surface and at different depths. There was mostly a linear relationship between Chla and b bp (700) during winter. During other seasons, the relationship between these two variables was better characterized by a power function (or a logarithmic function) in the lower layer of the DCM. The spatial and vertical relationships between the b bp (λ) and Chla and the corresponding variations in the types of particles described in this study provide parameters that can be used for accurate estimation of regional geochemical processes.