This paper considers the verification of non-standard CAN network topologies of the physical layer at high speed transmission rate (500.0Kbps and 1.0Mbps). These network topologies including single star, multiple stars, and hybrid topologies (multiple stars in combination with linear bus or with ring topology) are simulated by using behavior modeling language (VHDL-AMS) in comparison to measurement. Throughout the verification process, CAN transceiver behavioral model together with other CAN physical layer simulation components have been proved to be very accurate. The modeling of measurement environment of the CAN network is discussed, showing how to get the measurement and simulation results well matched. This demonstrates that the simulation solution is reliable, which is highly desired and very important for the verification requirement in CAN physical layer design. Last but not least, with the developed CAN measurement system, application layer is also proved working properly when implementing different non-standard topologies at high speed transmission rate.