In this work, we proposed and experimentally demonstrated a novel probabilistic shaping (PS) 64QAM-OFDM with low-density parity-check (LDPC)-coded modulation in a W-band RoF system using envelope detection. The proposed PS scheme has the advantages of no complex multiplication and division operations and low hardware implementation complexity. In our experiments, the TS-BWDM-based PS-64QAM DMT signals with a rate of 28.3-Gb/s transmission over 4-m wireless + 45-km SSMF transmission can be achieved. The system performance is investigated under one LDPC code rates (3/4) and two PS parameter values (k=3 and 9). The experimental results show that the receiver power sensitivity and the system fiber nonlinear effect tolerance can be significantly improved compared with uniformly-distributed signals.