The globally expanding doctoral education and the diminishing availability of academic job opportunities have prompted an increasing proportion of PhD graduates to seek employment beyond academia, drawing a growing scholarly interest. However, the existing literature on doctoral career pathways tends to be fragmented and dispersed, given the idiosyncratic individual and educational characteristics of doctorates grappling with the complex structural factors. To depict a comprehensive picture of the diversifying employment trajectories of doctorates across various geographical, disciplinary and sectoral contexts, this study conducts a systematic review, scouring 831 pertinent journal articles from the Web of Science. Following a set of inclusion criteria, 31 papers were ultimately selected to identify the key factors shaping employment trajectories of PhD graduates at structural (national supply and demand), institutional (employers' perceptions) and individual (doctorates' characteristics) levels. Drawing on the boundaryless and value‐based career theories, the authors develop a four‐dimension analytical framework, within which the findings of the 31 papers in East Asian and Western contexts are analysed. Overall, stakeholders in Western systems generally recognise the trend of PhD graduates securing non‐academic employment, whereas East Asian nations appear less receptive to this agenda. Meanwhile, due to their strong emphasis on research skills utilisation and employment stability, PhD graduates in certain economies find it challenging to pursue satisfying and successful careers, warranting increased attention. Building on the findings, we propose a four‐quadrat model in an effort to provide a tool for evaluating the capacity to absorb doctoral workforces of specific systems by categorising the doctoral professions. Highlighting shared patterns observed across various higher education systems and distinct trends prevalent in specific economies, this paper addresses key topics in doctoral education and doctorate employment literature such as labour market conditions, employment outcomes, job satisfaction, skills (mis)matches and sustainable careers.