Aims. Determination of branching fractions, cross sections and thermal rate coefficients for the dissociative recombination of CD 3 OCD 2 + (0-0.3 eV) and (CD 3 ) 2 OD + (0-0.2 eV) at the low relative kinetic energies encountered in the interstellar medium. Methods. The measurements were carried out using merged electron and ion beams at the CRYRING storage ring, Stockholm, Sweden.Results. For (CD 3 ) 2 OD + we have experimentally determined the branching fraction for ejection of a single hydrogen atom in the DR process to be maximally 7% whereas 49% of the reactions involve the break up of the COC chain into two heavy fragments and 44% ruptures both C-O bonds. The DR of CD 3 OCD 2 + is dominated by fragmentation of the COC chain into two heavy fragments. The measured thermal rate constants and cross sections are k(T ) = 1.7 ± 0.5 × 10 −6 (T/300) −0.77±0.01 cm 3 s −1 , σ = 1.2 ± 0.4 × 10 −15 (E cm [eV]) −1.27±0.01 cm 2 and k(T ) = 1.7 ± 0.6 × 10 −6 (T/300) −0.70 ± 0.02 cm 3 s −1 , σ = 1.7 ± 0.6 × 10 −15 (E cm [eV]) −1.20±0.02 cm 2 for CD 3 OCD 2 + and (CD 3 ) 2 OD + , respectively.