This paper attempts to develop a modified chemical percolation devolatilization (M-CPD) model that can include heat transfer, primary pyrolysis and the secondary cracking reactions of volatiles together to describe the pyrolysis of waste scrap tyre chip, as well as to examine the influence of operating conditions on the scrap tyre pyrolysis product yields. Such a study has yet to be conducted in the past, thereby leading to a large knowledge gap failing to understand the pyrolysis of the coarse feedstock appropriately. To validate the developed model, a number of operating parameters including reactor configurations, carrier gas compositions (argon and argon blended with CO2 and/or steam), scrap tyre chip size (0.5–15.0 mm), terminal pyrolysis temperature (400–800 °C) and heating rate (10 °C/min and 110 °C/min) were examined in a lab-scale fixed-bed pyrolyser, with a particular focus on the secondary cracking extents of the liquid tar.