Carboxymethylcellulose (CMC, DSCM = 1) was partially hydrophobized in order to prepare polymeric surfactants by the transesterification reaction using the methyl ester of the fatty acid complex of rapeseed oil (MERO). The chemical modification was performed in different reaction media (i) DMF/TSA and (ii) H2O/DMF with and without K2CO3 as catalyst, at various reaction conditions and using microwave radiation with controlled power as heating source. The obtained MERO-hydrophobized CMC (MH-CMC) comprising mixed fatty acyl esters were characterized by FT-IR and NMR spectroscopic techniques, which indicated a very low degree of esterification (DS < 0.1). The derivatives showed, in spite of moderate surface tension-lowering effects, excellent emulsifying activity for 'oil in water' type emulsions as well as good performance properties including washing power and antiredeposition efficiency. The results suggested that surface-active MH-CMC derivatives can be prepared under microwave heating at reaction times in the range of several minutes, what is a great advantage in comparison to transesterification reactions lasting up to 6 h at conventional heating. The novel CMC esters represent biodegradable polymeric surfactants with potential applications in manufacture of consumer products and in industrial processes.