The bubble nucleation mechanism on a cavity-free micro line heater surface was studied by using the molecular cluster model. A finite difference numerical scheme for the three-dimensional transient conduction equation for the liquid was employed to estimate the superheated volume where homogeneous bubble nucleation could occur due to heat diffusion from the heater to the liquid. Calculation results revealed that bubble formation on the heater is possible when the temperature at the hottest point in the heater is greater than the superheat limit of the liquid by 6°C–12°C, which is in agreement with the experimental results. Also it was found that the classical bubble nucleation theory breaks down near the critical point where the radius of the critical bubble is below 100 nm.