How to find if native dll is compiled as x64 or x86?

You can use dumpbin too. Use the /headers or /all flag and it's the first file header listed.

dumpbin /headers cv210.dll

64-bit:

Microsoft (R) COFF/PE Dumper Version 10.00.30319.01
Copyright (C) Microsoft Corporation.  All rights reserved.


Dump of file cv210.dll

PE signature found

File Type: DLL

FILE HEADER VALUES
            8664 machine (x64)
               6 number of sections
        4BBAB813 time date stamp Tue Apr 06 12:26:59 2010
               0 file pointer to symbol table
               0 number of symbols
              F0 size of optional header
            2022 characteristics
                   Executable
                   Application can handle large (>2GB) addresses
                   DLL

32-bit:

Microsoft (R) COFF/PE Dumper Version 10.00.30319.01
Copyright (C) Microsoft Corporation.  All rights reserved.


Dump of file acrdlg.dll

PE signature found

File Type: DLL

FILE HEADER VALUES
             14C machine (x86)
               5 number of sections
        467AFDD2 time date stamp Fri Jun 22 06:38:10 2007
               0 file pointer to symbol table
               0 number of symbols
              E0 size of optional header
            2306 characteristics
                   Executable
                   Line numbers stripped
                   32 bit word machine
                   Debug information stripped
                   DLL

'find' can make life slightly easier:

dumpbin /headers cv210.dll |find "machine"
        8664 machine (x64)