Methanol fuelled high temperature polymer electrolyte membrane fuel cell (HTPEMFC) power systems are promising as the next generation of vehicle engines, efficient and environmentally friendly. Currently, their performance still needs to be improved and they still rely on a large Li-ion battery for system startup. In this paper, to handle these two issues, the potential of thermoelectric (TE) devices applied in a HTPEMFC power system has been preliminarily evaluated. Firstly, right after the fuel cell stack or the methanol reformer, thermoelectric generators (TEGs) are embedded inside a gas-liquid heat exchanger to jointly form a heat recovery subsystem for electricity production. It is calculated that the recovered power can increase the system efficiency and mitigate the dependence on Li-ion battery during system startup. To further improve the TEG subsystem performance, a finite-difference model is then employed and two main parameters are identified. Secondly, TE coolers are integrated into the methanol steam reformer to regulate heat fluxes herein and improve the system dynamic performance. Similar modification is also done on the evaporator to improve its dynamic performance as well as to reduce the heat loss during system startup. The results demonstrate that the TE-assisted heat flux regulation and heat-loss reduction can also effectively help solve the abovementioned two issues. The preliminary analysis in this paper shows that a TE device application inside HTPEMFC power systems is of great value and worthy of further study.