•Implementation costs are a more relevant constraint to afforestation than opportunity costs.•Financial incentives for afforestation are constrained by market access and market prices.•Carbon-neutral and food multi-oriented land policies need further exploration.•Collaboration among global carbon markets can enhance CO2 removal efficiency. Afforestation is a promising nature-based climate solution for mitigating climate change, but it is subject to a complex web of biophysical, cost-benefit, market, and policy processes. Although its biophysical feasibility has been established, the cost, market, and policy constraints that affect climate change mitigation through afforestation are still unclear. Here, we estimate such cost, market, and policy constraints on the basis of biophysical feasibility. Our findings reveal that implementation costs are a more relevant constraint than opportunity costs on mitigating climate change through afforestation. The China Certified Emission Reduction market currently provides only a 0.308 % incentive for climate change mitigation through afforestation, due to market access constraints. The current market prices of China Certified Emission Reduction, China Carbon Emissions Trading Exchange, and Nature Based Carbon Offset in Voluntary Carbon Market constrain 88.15 %, 87.95 %, and 85.75 % of CO2 removal actions through afforestation, compared to the carbon price scenario (US$62.97 tCO2-1) of the EU Emissions Trading System. Moreover, land policy under the scenarios of prohibiting conversion of cultivated land to forest and forest restoration in degraded areas exhibit 8.87–29.59 % and 65.16–74.10 % constraints, respectively, on mitigating climate change through afforestation compared to land-use freedom conversion scenarios from 2020 to 2060. Thus, enhancing the incentive price of CO2 removal, addressing the market access barrier, strengthening cooperation between global carbon markets, and exploring carbon–neutral and food multi-oriented land policies can be valuable sources of mitigation efforts over the next 40 years.