Technological determinism is a recurrent feature in debates concerning changes in economy and work and has resurfaced sharply in the discourse around the ‘fourth industrial revolution’. While a number of authors have, in recent years, critiqued the trend, this article is distinctive in arguing that foundational labour process analysis provides the most effective source of an alternative understanding of the relations between political economy, science, technology and work relations. The article refines and reframes this analysis, through an engagement with critical commentary and research, developing the idea of a political materialist approach that can reveal the various influences on, sources of contestation and levels of strategic choices that are open to economic actors. A distinction is made between ‘first order’ choices, often about adoption at aggregate level and ‘second order’ choices mainly concerned with complex issues of deployment. This framework is then applied to the analysis of case studies of the call centre labour process and digital labour platform, functioning as illustrative scenarios. It is argued that the nature of techno-economic systems in the ‘digital era’ open up greater opportunities for contestation.