Cycling is considered an environmentally-friendly mode of transport that offers many personal benefits including health, affordability and flexibility of travel. To encourage more people to cycle, especially in contexts where cycle ownership and ridership is considerably low, requires understanding the underlying motivations and barriers to cycling. This study models the behavioural influences of individuals’ (N = 348) intended adoption of cycling to work in the Kumasi metropolis in Ghana, West Africa. It deploys the theory of planned behaviour (TPB) to explore the extent to which socio-psychological constructs namely; Attitude, perceived behavioural (PBC) and subjective norm (SN) influence intended adoption of cycling as work travel mode. The influence of participants’ perception of their physical environment as well as their personal characteristics, cycling history and bicycle ownership are also examined. Results of an SEM analysis showed that among the TPB constructs, PBC (i.e. perception of self-confidence, personal control and ease of cycling) had the strongest positive and direct effect on participants’ intention to cycle to work. Negative associations were found between attitude and SN and SN and PBC, suggesting that belief about the prestige of cycling relative to other modes, and approval of society and significant others of cycling, influenced perception of control and confidence as well as attitude with respect to cycling. Also, participants’ perception of their environment including traffic-lights, traffic volume and congestion, as well as bicycle ownership and frequency of use, increased intended adoption of cycling. Finally, being female decreased the likelihood of intended cycling adoption. Cycling promotion interventions could be anchored on people’s already strong perceived control and confidence to cycle while addressing negative perceptions and attitudes towards cycling as a mainstream transport mode.