Aiming at the problems of small thermal power units and biomass mixed combustion units with small generation loads and insufficient primary frequency modulation capability, which cannot be connected to the virtual power plant, this paper adopts a variety of flexibility retrofit methods for the units and explores the peak load capability of the units. Then, multiple units are coupled, and the unit coupling scheme with better economy and environmental protection is screened using comprehensive evaluation indexes. While evaluating the peaking load space of multiple unit coupling, the units’ primary frequency regulation capability and new energy consumption capability are improved. According to the calculation results, the low-pressure cylinder zero-output retrofit has the largest peaking potential among different technical paths, in which unit #3 has 27.55 MW of peaking space. The compression heat pump decoupling retrofit has the best economy, in which the daily profit of unit #3 increases from 0.93 to 1.02 million CNY with an increase of 0.09 million CNY. After the unit has been retrofitted with steam extraction, the three units can be coupled to meet the national feed-in standards. The multiple unit coupling can accommodate up to 203.44 MW of other energy sources while meeting the standard.