The assessment and diagnosis of lower limb peripheral arterial occlusive disease (PAOD) is important since it can lead progressively to disabling claudication, ischaemic rest pain and gangrene. Historically, the first assessment has been palpation of the peripheral pulse since it can become damped, delayed and diminished with disease. In this study we investigated the clinical value of objective photoplethysmography (PPG) pulse measurements collected simultaneously from the right and left great toes to diagnose disease in the lower limbs. In total, 63 healthy subjects and 44 patients with suspected lower limb disease were studied. Pulse wave analysis techniques extracted timing, amplitude and shape characteristics for both toes and for right-to-left toe differences. Normative ranges of pulse characteristics were then calculated for the healthy subject group. The relative diagnostic values of the different pulse features for detecting lower limb arterial disease were determined, referenced to the established ankle-brachial pressure index (ABPI) measurement. The ranges of pulse characteristics and degree of bilateral similarity in healthy subjects were established, and the degrees of pulse delay, amplitude reduction, and damping and bilateral asymmetry were quantified for different grades of disease. When pulse timing, amplitude and shape features were ranked in order of diagnostic performance, the shape index (SI) gave substantial agreement with ABPI (>90% accuracy, kappa 0.75). SI also detected higher grade disease, for legs with an ABPI less than 0.5, with a sensitivity of 100%. The simple-to-calculate timing differences between pulse peaks produced a diagnostic accuracy of 88% for all grades of arterial disease (kappa 0.70), and 93% for higher grade disease (kappa 0.77). These contrasted with the limited discriminatory value of PPG pulse amplitude. The low-cost and simplicity of this optical-based technology could offer significant benefits to healthcare, such as in primary care where non-invasive, accurate and simple-to-use (de-skilled) diagnostic techniques are desirable.