The homologous series of high-molecular weight dimethylalkanes (HMWDMAs) with either odd- or even-numbered carbon chains in the range from C19-20 to C30-31 have been identified in organic matter from recent and partially lithified deposits of Siberia and the Russian Platform by chromatography-mass spectrometry. The first homologous series is represented by even-numbered 3,4-HMWDMAs followed by the alternation of odd-numbered 3,5-HMWDMAs, even-numbered 3,6-HMWDMAs, and odd-numbered 3,7-HMWDMAs. The most abundant are 3,7-dimethylalkanes. The microbial origin of high-molecular weight dimethylalkanes is the most likely explanation for their presence in the fossil organic matter. The precursors of HMWDMAs might have been tetra- and diether lipids of archaea and bacteria. It is assumed that HMWDMAs and other immature hydrocarbons from great depths (SV-27 and SG-6 superdeep boreholes) result from the decomposition of asphaltenes, which occluded the related compounds inside their structure during the early stages of generation and carried them unchanged throughout the "oil window".