Magnetic resonance imaging (MRI) relaxometry and diffusion methods were used to highlight the instability mechanisms of oil-in-water Pickering emulsions stabilized by cellulose nanofibers (CNFs). Four different Pickering emulsions using different oils (n-dodecane and olive oil) and concentrations of CNFs (0.5 and 1.0 wt %) were systematically investigated over a period of one month after emulsification. The separation into a free oil, emulsion layer, and serum layer and the distribution of flocculated/coalesced oil droplets in several hundred micrometers were captured in MR images using fast low-angle shot (FLASH) and rapid acquisition with relaxation enhancement (RARE) sequences. The components of the Pickering emulsions (e.g., free oil, emulsion layer, oil droplets, and serum layer) were observable by different voxelwise relaxation times and apparent diffusion coefficients (ADCs) and reconstructing in the apparent T1, T2, and ADC maps. The mean T1, T2, and ADC of the free oil and serum layer corresponded well with MRI results for pure oils and water, respectively. Comparing the relaxation properties and translational diffusion coefficients of pure dodecane and olive oil obtained from NMR and MRI resulted in similar T1 and ADC but significantly different T2 depending on the sequence used. The diffusion coefficients of olive oil measured by NMR were much slower than dodecane. The ADC of the emulsion layer for dodecane emulsions did not correlate with the viscosity of the emulsions as the CNF concentration increased, suggesting the effects of restricted diffusion of oil/water molecules due to droplet packing.