Photothermal therapy (PTT) as a relatively new cancer treatment method has attracted worldwide attention. Previous research on PTT has focused on its therapy efficiency and selectivity. The early prognosis of PTT, which is pivotal for the assessment of the treatment and the therapy stratification, however, has been rarely studied. In the present study, we investigated diffusion-weighted magnetic resonance imaging (DW-MRI) as a tool for therapy monitoring and early prognosis of PTT. To this end, we injected PEGylated graphene oxide (GO-PEG) or iron oxide deposited graphene oxide (GO-IONP-PEG) to 4T1 tumor models and irradiated the tumors at different drug-light intervals to induce PTT. For GO-IONP-PEG injected animals, we also included therapy arms where an external magnetic field was applied to the tumors to improve the delivery of the nanoparticle transducers. DW-MRI was performed at different time points after PTT and the tumor apparent diffusion coefficients (ADCs) were analyzed and compared. Our studies show that photothermal agents, magnetic guidance, and drug-light intervals can all affect PTT treatment efficacy. Impressively, ADC value changes at early time points after PTT (less than 48 h) were found to be well-correlated with tumor growth suppression that was apparent days or weeks later. The changes were most sensitive to conditions that can extend the survival for more than 4 weeks, in which cases the 48 h ADC values were increased by more than 80%. These studies demonstrate for the first time that DW-MRI can be an accurate prognosis tool for PTT, suggesting an important role it can play in the future PTT evaluation and clinical translation of the modality.