Highly complex cognitive works require more brain power. The productivity of a person suffers due to this strain, which is sometimes referred to as a mental burden or psychological load. A person's mental health and safety in high-stress working conditions can be improved with the help of mental workload assessment. A photoplethysmogram (PPG) signal is a non-invasive and easily acquired physiological signal that contains information related to blood volume changes in the micro-vascular bed of tissues and can indicate psychologically relevant information to assess a person's mental workload (MW). An individual under a high MW possesses an increase in sympathetic nervous system activity, which results in morphological changes in the PPG waveform. In this work, a time-frequency analysis framework is developed to capture these distinguishing PPG features for the automatic assessment of MW. In particular, a cross-wavelet coherence (WTC) approach is proposed to extract simultaneous time-frequency information of the PPG during MW relative to the resting PPG. The suggested technique is validated on a publicly available data set of 22 healthy individuals who took part in an N-back task with PPG recording. Under three different fixed window lengths, images are obtained using WTC between PPG records during N-back task activity and rest. The images are used further to obtain PPG classification in two broad classes of low and high MW using a customized pre-trained Inception-V3 model. The best validation and test accuracy of 93.86% and 93.07%, respectively obtained in the window setting of 1200 samples used for WTC image creation.