The Smoluchowski equation has become a fundamental equation in nanoparticle processes since it was proposed in 1917, whereas the achievement of its analytical solution remains a challenging issue. In this work, a new analytical solution, which is absolutely different from the conventional asymptotic solutions, is first proposed and verified for non-self-preserving nanoparticle systems in the free molecular regime. The Smoluchowski equation is first converted to the form of moment ordinary differential equations by the performance of Taylor expansion method of moments and subsequently resolved by the separate variable technique. In the derivative, a novel variable, g = m0m2/m12, where m0, m1 and m2 are the first three moments, is first revealed which can be treated as constant. Three specific models are proposed, two with a constant g (an Analytical Model with Constant g (AMC), and a Modified Analytical Model with Constant g (MAMC)), and another with varying g (a finite Analytical Model with Varying g (AMV)). The AMC model yields significant errors, while its modified version, i.e., the MAMC model, is able to produce highly reliable results. The AMV is verified to have the capability to solve the Smoluchowski equation with the same precision as the numerical method, but an iterative procedure has to be employed in the calculation.