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In this paper, for \\(-1<\\alpha<1\\) and \\(1\\leq p,\\,q\\leq \\infty\\), the authors introduce a new class of Besov spaces \\(B_{p,q}^{\\alpha,L}(\\mathcal{X})\\) associated with the operator \\(L\\). This new Besov space \\(B_{p,q}^{\\alpha,L}(\\mathcal{X})\\) is defined to be the space of all elements belonging to some ``distribution space'' with the norm  \\[ \\|f\\|_{B_{p,q}^{\\alpha,L}(\\mathcal{X})}:=\\left\\{\\int_{0}^\\infty \\left( t^\\alpha\\left\\| tLe^{-tL} (f)\\right\\|_{L^p(\\mathcal{X})} \\right)^q\\frac{dt}{t}\\right\\}^{1/q}<\\infty, \\]  which generalizes the notion of the classical Besov space and has wide applications.  One of the main aims of this paper is to find the relationship between the classical and the new Besov spaces. By assuming that \\(L\\) has some conservation property, the authors show that the classical Besov space \\(B_{p,q}^{\\alpha}(\\mathbb R^n)\\) is continuously embedded in \\(B_{p,q}^{\\alpha,L}(\\mathbb R^n)\\). Moreover, if the heat kernels \\(\\{p_t(x,\\,y)\\}_{t>0}\\) of \\(\\{e^{-tL}\\}_{t>0}\\) further satisfy some H\u00f6lder continuity, the authors prove the equivalence \\(B_{p,q}^{\\alpha}(\\mathbb R^n)=B_{p,q}^{\\alpha,L}(\\mathbb R^n)\\). Also, by establishing four different Calder\u00f3n reproducing formulas, which are of independent interest, the authors obtain many basic properties of \\(B_{p,q}^{\\alpha,L}(\\mathcal{X})\\), such as the embedding theorem, some norm equivalences and the boundedness of the fractional integral \\(L^{-\\gamma}\\) for \\(\\gamma\\in(0,\\,1)\\).  As an application, when the operator \\(L:=-\\Delta+V\\) is a Schr\u00f6dinger operator on the Euclidean space \\(\\mathbb{R}^n\\) with the nonnegative potential \\(V\\) satisfying some reverse H\u00f6lder estimates, the authors study the Besov space \\(B_{1,1}^{0,L}(\\mathbb{R}^n)\\) and prove that the classical Besov space \\(B_{1,1}^{0}(\\mathbb{R}^n)\\) is strictly contained in \\(B_{1,1}^{0,L}(\\mathbb{R}^n)\\). Moreover, by using one of the Calder\u00f3n reproducing formulas, a new molecular characterization of \\(B_{1,1}^{0,L}(\\mathbb{R}^n)\\) is also 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