Deep learning (DL) has recently attracted attention for data processing in positron emission tomography (PET). Attenuation correction (AC) without computed tomography (CT) data is one of the interests. Here, we present, to our knowledge, the first attempt to generate an attenuation map of the human head via Sim2Real DL-based tissue composition estimation from model training using only the simulated PET dataset. The DL model accepts a two-dimensional non-attenuation-corrected PET image as input and outputs a four-channel tissue-composition map of soft tissue, bone, cavity, and background. Then, an attenuation map is generated by a linear combination of the tissue composition maps and, finally, used as input for scatter+randomestimation and as an initial estimate for attenuation map reconstruction by the maximum likelihood attenuation correction factor (MLACF), i.e., the DL estimate is refined by the MLACF. Preliminary results using clinical brain PET data showed that the proposed DL model tended to estimate anatomical details inaccurately, especially in the neck-side slices. However, it succeeded in estimating overall anatomical structures, and the PET quantitative accuracy with DL-based AC was comparable to that with CT-based AC. Thus, the proposed DL-based approach combined with the MLACF is also a promising CT-less AC approach.