Non-invasive assessment of haemoglobin (Hb) level in blood is a hot spot in the point-of-care biomedical diagnostics. Several optical methods are suggested as a solution, some of them being approved for clinical use. Still, there is no consensus on the accuracy of optical techniques, the quality of Hb assessment on different tissue sites, and on the ability of combined use of several optical techniques to improve the quality of Hb level prediction. In this work we examined the capabilities of two optical techniques—diffuse reflectance spectroscopy and RGB-imaging of the skin and fingernails areas—in detecting low blood Hb level. The test sample consisted of 240 adult volunteers with 70 volunteers exhibiting Hb level lower than 120 g/L. We show that using simple descriptors of the diffuse reflectance spectrum of the forearm skin and fingernails is applicable for predicting low blood Hb concentration (ROC-AUC = 0.84 ± 0.08), while RGB-imaging shows similar performance when applied to the fingernail areas (ROC-AUC = 0.83 ± 0.07), which can be considered perspective for clinical use and screening properties. We also report that while the joint use of predictions from two optical methods slightly improves the accuracy of non-invasive Hb level assessment (ROC-AUC = 0.86 ± 0.07), the effect is not as high as one might expect from combining predictions of truly independent modalities, indicating the limit of the accuracy one can expect with multimodal optical approach. We review this case and propose possible solutions towards more sensitive non-invasive optical determination of hemoglobin.